WO2005113704A2 - Luminescent compounds with carbene ligands - Google Patents

Luminescent compounds with carbene ligands Download PDF

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Publication number
WO2005113704A2
WO2005113704A2 PCT/US2005/017336 US2005017336W WO2005113704A2 WO 2005113704 A2 WO2005113704 A2 WO 2005113704A2 US 2005017336 W US2005017336 W US 2005017336W WO 2005113704 A2 WO2005113704 A2 WO 2005113704A2
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WIPO (PCT)
Prior art keywords
aryl
heteroaryl
group
alkyl
aralkyl
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PCT/US2005/017336
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French (fr)
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WO2005113704A3 (en
Inventor
Mark E. Thompson
Arnold Tamayo
Peter Djurovich
Tissa Sajoto
Stephen R. Forrest
Peter B. Mackenzie
Robert Walters
Jason Brooks
Xiao-Chang Li
Bert Alleyne
Jui-Yi Tsai
Chun Lin
Bin Ma
Michael S. Barone
Raymond Kwong
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The University Of Southern California
The Trustees Of Princeton University
Universal Display Corporation
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Priority claimed from US10/849,301 external-priority patent/US7491823B2/en
Priority claimed from US10/880,384 external-priority patent/US7393599B2/en
Priority claimed from US11/032,941 external-priority patent/US7582365B2/en
Priority claimed from US11/032,885 external-priority patent/US7534505B2/en
Priority claimed from US11/032,887 external-priority patent/US7601436B2/en
Priority claimed from US11/032,950 external-priority patent/US7279704B2/en
Priority claimed from US11/032,721 external-priority patent/US7445855B2/en
Priority claimed from US11/032,836 external-priority patent/US7154114B2/en
Priority claimed from US11/031,078 external-priority patent/US7655323B2/en
Priority claimed from US11/032,739 external-priority patent/US7598388B2/en
Application filed by The University Of Southern California, The Trustees Of Princeton University, Universal Display Corporation filed Critical The University Of Southern California
Publication of WO2005113704A2 publication Critical patent/WO2005113704A2/en
Publication of WO2005113704A3 publication Critical patent/WO2005113704A3/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene

Definitions

  • the claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Princeton University, The University of Southern California and Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.
  • the present invention relates to organic light emitting devices (OLEDs), and more specifically to phosphorescent organic materials used in such devices. More specifically, the present invention relates to carbene-metal complexes incorporated into OLEDs.
  • Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
  • OLEDs organic light emitting devices
  • the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
  • organic includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic optoelectronic devices.
  • Small molecule refers to any organic material that is not a polymer, and "small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the "small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety.
  • the core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter.
  • a dendrimer may be a "small molecule," and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
  • a small molecule has a well-defined chemical formula with a single molecular weight, whereas a polymer has a chemical formula and a molecular weight that may vary from molecule to molecule.
  • organic includes metal complexes of hydrocarbyl and heteroatom-substituted hydrocarbyl ligands. [0006] OLEDs make use of thin organic films that emit light when voltage is applied across the device.
  • OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting.
  • OLED materials and configurations are described in U.S. Patent Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entireties.
  • OLED devices are generally (but not always) intended to emit light through at least one of the electrodes, and one or more transparent electrodes may be useful in organic opto-electronic devices.
  • a transparent electrode material such as indium tin oxide (ITO)
  • ITO indium tin oxide
  • a transparent top electrode such as disclosed in U.S. Patent Nos.
  • the top electrode does not need to be transparent, and may be comprised of a thick and reflective metal layer having a high electrical conductivity.
  • the bottom electrode may be opaque and / or reflective. Where an electrode does not need to be transparent, using a thicker layer may provide better conductivity, and using a reflective electrode may increase the amount of light emitted through the other electrode, by reflecting light back towards the transparent electrode.
  • Fully transparent devices may also be fabricated, where both electrodes are transparent. Side emitting OLEDs may also be fabricated, and one or both electrodes may be opaque or reflective in such devices.
  • top means furthest away from the substrate
  • bottom means closest to the substrate.
  • the bottom electrode is the electrode closest to the substrate, and is generally the first electrode fabricated.
  • the bottom electrode has two surfaces, a bottom surface closest to the substrate, and a top surface further away from the substrate.
  • a first layer is described as "disposed over” a second layer
  • the first layer is disposed further away from substrate.
  • a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
  • solution processible means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
  • a first "Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is "greater than” or "higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level.
  • IP ionization potentials
  • a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative).
  • a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative).
  • the LUMO energy level of a material is higher than the HOMO energy level of the same material.
  • a "higher" HOMO or LUMO energy level appears closer to the top of such a diagram than a "lower” HOMO or LUMO energy level.
  • the carbene ligand has been well known in organometallic chemistry, and is used to generate a wide range of thermally stable catalytic materials.
  • the carbene ligands have been employed both as active groups, directly engaged in the catalytic reactions, and serving a role of stabilizing the metal in a particular oxidation state or coordination geometry.
  • applications of carbene ligands are not well known in photochemistry.
  • An object of the invention is to provide a class of organic emissive compounds having improved stability.
  • existing compounds do not include compounds that are stable emitters for high energy spectra, such as a blue spectra.
  • An object of the invention is to provide a class of organic emissive compounds that can emit light with various spectra, including high energy spectra such as blue, in a stable manner.
  • An organic light emitting device has an anode, a cathode and an organic layer disposed between the anode and the cathode.
  • the organic layer comprises a compound further comprising one or more carbene ligands coordinated to a metal center.
  • the organic layer comprises a compound having at least one zwitterionic carbon donor ligand.
  • he organic layer comprises a host and a dopant
  • the host comprises a compound having at least one carbene atom coordinated to iridium, and the compound has the structure:
  • the organic layer comprises a reversibly reducible metal complex of a redox active metal center and at least one ligand, where, in a reduced state, an extra electron is localized on the metal center.
  • the redox active metal complex i.e., the reversibly reducible metal complex, may function as an ETL and/or as a host for an emissive material.
  • Preferred reducible metal complexes in accordance with the invention are of Formula I
  • Redox active metal complexes in accordance with the invention include, but are not limited to, reversibly reducible metal complexes of formula:
  • the organic layer comprises a carbene ligand bound to a metal center, wherein the resulting metal-carbene complex is cationic.
  • the organic layer comprises at least one tridentate ligand bound to a metal center through at least one carbene-metal bond.
  • the organic layer comprises two tridentate ligands, which may be the same or different, bound to the metal center, wherein at least one of the tridentate ligands has a carbene-metal bond. More preferably, the organic layer comprises an emissive material having the formulae:
  • the organic layer comprises an organometallic compound further comprising a macrocyclic ligand coordinated to a metal center.
  • the macrocyclic ligand is planar.
  • the macrocyclic ligand is a tetradentate ligand.
  • the macrocyclic tetradentate ligand comprises two 5-membered rings and two 6-membered rings, each coordinated to the metal center.
  • the organic layer comprises a macrocyclic compound having the structures:
  • a process for preparing a compound having the formula L 2 IrL' comprises:
  • a process for preparing a compound having the formula comprises:
  • step (a) combining L with an organic solvent, wherein L is a suitable carbene ligand precursor; (b) maintaining the mixture of step (a) at a temperature from about 175°C to less
  • a process for preparing a compound with the formula L 3 Ir is also provided in another aspect. This process comprises:
  • Fig. 1 shows an organic light emitting device having separate electron transport, hole transport, and emissive layers, as well as other layers.
  • Fig. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.
  • Fig. 3 shows the 1H NMR spectra of mer-(F 2 ppz) 2 Ir(l -Ph-3 -Me-imid) in
  • Fig. 4 shows the 1H NMR spectra of mer-(tpy) 2 Ir(l -Ph-3 -Me-imid) in CDC1 3 .
  • Fig. 5 shows the 1H NMR spectra of fac-(tpy) 2 Ir(l -Ph-3 -Me-imid) in CDC1 3 .
  • Fig. 6 shows the plot of current ( ⁇ A) vs. voltage (V) of amer-(tpy) 2 Ir(l-Ph-3-
  • Fig. 7 shows the plot of current ( ⁇ A) vs. voltage (V) of a fac-(tpy) 2 Ir(l -Ph-3-
  • Fig. 8 shows the absorption spectra of fac-(tpy) 2 Ir(l -Ph-3 -Me-imid) and mer-
  • Fig. 9 shows the emission spectra of mer-(tpy) 2 Ir(l -Ph-3 -Me-imid) in 2-
  • MeTHF at room temperature and at 77K exhibits lifetimes of 1.7 ⁇ s at room temperature and 3.3 ⁇ s at 77K.
  • Fig. 10 shows the emission spectra of fac-(tpy) 2 Ir(l -Ph-3 -Me-imid) in 2-
  • MeTHF at room temperature and at 77K exhibits lifetimes of 1.7 ⁇ s at room temperature and 3.3 ⁇ s at 77K.
  • Fig. 11 shows the 1H NMR spectra of [(l-Ph-3-Me-imid) 2 IrCl] 2 in CDC1 3 .
  • Fig. 12 shows the 1H NMR spectra of (l-Ph-3-Me-imid) 2 Ir(t-Bu-bpy) + in
  • Fig. 13 shows the absorption spectra of (l-Ph-3-Me-imid) 2 Ir(t-Bu-bpy)+ in
  • Fig. 14 shows the emission spectra of (l-Ph-3-Me-imid) 2 Ir(t-Bu-bpy) + in 2-
  • Fig. 15 shows the 1H NMR spectra of mer-Ir(l-Ph-3-Me-imid) 3 in CDC1 3 .
  • Fig. 16 shows the 13 C NMR spectra of mer-Ir(l-Ph-3-Me-imid) 3 in CDC1 3 .
  • Fig. 17 shows the plot of current ( ⁇ A) vs. voltage (V) of a mer-Ir(l-Ph-3-Me- imid) device with ferrocene as an internal reference.
  • a solvent of DMF with 0.1M is used.
  • Fig. 18 shows the emission spectra of mer-Ir(l-Ph-3-Me-imid) 3 in 2-MeTHF at room temperature and at 77K.
  • Fig. 19 shows the 1H NMR spectra of fac-Ir(l-Ph-3-Me-imid) 3 in CDC1 3 .
  • Fig. 20 shows the absorption spectra of fac-Ir(l-Ph-3-Me-imid) 3 in CH C1 .
  • Fig. 21 shows the emission spectra of fac-rr(l-Ph-3-Me-imid) 3 in 2-MeTHF at room temperature and at 77K.
  • the device exhibits lifetimes of 0.50 ⁇ s at room temperature and 6.8 ⁇ s at 77K.
  • Fig. 22 shows the 1H NMR spectra of 1 -Ph-3 -Me-benzimid in CDC1 3 .
  • Fig. 23 shows the 1H NMR spectra of fac-Ir(l -Ph-3 -Me-benzimid) 3 in CDC1 3 .
  • Fig. 24 shows the plot of current (mA) vs. voltage (V) of a fac-Ir(l-Ph-3-Me- benzimid) device with ferrocene as an internal reference. A solvent of anhydrous DMF is used.
  • Fig. 25 shows the emission spectra of fac-Ir(l-Ph-3-Me-benzimid) 3 in 2-
  • the device emits a spectrum at CIE 0.17, 0.04.
  • Fig. 26 shows the emission spectra of (Ir-Fl-Me-imid) 3 in 2-MeTHF at room temperature and at 77K.
  • the device exhibits lifetimes of 5 ⁇ s at room temperature and 35 ⁇ s at 77K.
  • Figure 27 shows the external quantum efficiency vs. current density of examples 20-21 and comparative example 1.
  • Figure 28 shows the electroluminescence spectra of examples 20-21 and comparative example 1 at 10 mA/cm .
  • Figure 29 shows the operational stability of example 20 vs comparative example 1.
  • Figure 30 shows the external quantum efficiency vs. current density of examples 22-25.
  • Figure 31 shows the electroluminescence spectra of examples 22-25.
  • Figure 32 shows the external quantum efficiency vs. current density of examples 26-29.
  • Figure 33 shows the electroluminescence spectra of examples 26-29.
  • Figure 34 shows the external quantum efficiency vs. current density of examples 30 and 31.
  • Figure 35 shows the electroluminescence spectra of examples 30 and 31.
  • Figure 36 shows the external quantum efficiency vs. current density of example 32.
  • Figure 37 shows the electroluminescence spectra of example 32.
  • Figure 38 shows the external quantum efficiency vs. current density of example 33.
  • Figure 39 shows the electroluminescence spectra of example 33.
  • Figure 40 shows the external quantum efficiency vs. current density of example 34 and 35.
  • Figure 41 shows the electroluminescence spectra of example 34 and 35.
  • Figure 42 shows the subtracted EL spectra of example 34 from example 35.
  • Figure 43 shows the quantum efficiency vs. current density for comparative example 4.
  • Figure 44 shows the normalized electroluminescent spectra for comparative example 4.
  • Fig. 45 shows plots of current vs. voltage for device
  • Fig. 46 shows plots of quantum efficiency vs. current density for device
  • Fig. 47 shows plots of the electroluminescent spectra of device
  • Fig. 48 shows plots of current vs. voltage for device
  • Fig. 49 shows plots of quantum efficiency vs. current density for device
  • Fig. 50 shows plots of the electroluminescent spectra of device
  • Fig. 51 shows plots of current vs. voltage for device
  • Fig. 52 shows plots of quantum efficiency vs. current density for device
  • Fig. 53 shows plots of the electroluminescent spectra of device
  • Fig. 54 shows plots of current vs. voltage for device
  • Fig. 55 shows plots of quantum efficiency vs. current density for
  • Fig. 56 shows plots of the electroluminescent spectra of
  • Fig. 57 shows plots of current vs. voltage for device
  • Fig. 58 shows plots of quantum efficiency vs. current density for device
  • Fig. 59 shows plots of the electroluminescent spectra of device
  • Fig. 60 shows plots of current vs. voltage for device
  • Fig. 61 shows plots of quantum efficiency vs. current density for device
  • Fig. 62 shows plots of the electroluminescent spectra of device
  • Fig. 63 shows plots of current vs. voltage for device
  • Fig. 64 shows plots of quantum efficiency vs. current density for device
  • Fig. 65 shows plots of the electroluminescent spectra of device
  • Fig. 66 shows plots of the plot of operation lifetime of device
  • Fig. 67 shows plots of current vs. voltage of device CuPc(l 00 A)/NPD(300
  • Fig. 68 shows plots of quantum efficiency vs. current density for device
  • Fig. 69 shows the electroluminescent spectra for device CuPc(100
  • Fig. 70 shows plots of current vs. voltage of device CuPc(100 A)/NPD(300
  • TCTA(100 A)/UGH5 Dopant Q (300 A,12%)/BA1Q(400 A).
  • Fig. 71 shows plots of quantum efficiency vs. current density for device
  • Fig. 72 shows the electroluminescent spectra for device CuPc(100
  • Fig. 73 shows plots of operational lifetime of device CuPc(100 A)/NPD(300
  • Dopant Q 300 A,6%/BA1Q(400 A) and device CuPc(100 A)/NPD(300 A)/mCP:
  • Dopant Q 300 A,6%
  • HPT(100 A)/BA1Q(400 A) measured at 5 mA cm 2 .
  • Figure 74 shows plots of the current density vs. voltage for device Examples
  • Fig. 75 shows plots of the quantum efficiency vs. current density for device
  • Fig. 76 shows plots of the electroluminescent spectra for device Examples 56 and 57.
  • Fig. 77 shows plots of current density vs. voltage for device Examples 58 and
  • Fig. 78 shows plots of the quantum efficiency vs. current density for device
  • Fig. 79 shows plots of the electroluminescent spectra for device Examples 58 and 59.
  • Fig. 80 shows plots of operation lifetime of device Examples 56, 58, and 59.
  • Fig. 81 shows the emission spectra for compound Osl.
  • Fig. 82 shows the emission spectra for compound Os2.
  • Fig. 83 shows the room temperature emission spectrum for compound Pt 151.
  • an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode.
  • the anode injects holes and the cathode injects electrons into the organic layer(s).
  • the injected holes and electrons each migrate toward the oppositely charged electrode.
  • an "exciton” which is a localized electron-hole pair having an excited energy state, is formed.
  • Light is emitted when the exciton relaxes via a photoemissive mechanism.
  • the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
  • the initial OLEDs used emissive molecules that emitted light from their singlet states ("fluorescence") as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
  • Phosphorescence may be referred to as a "forbidden" transition because the transition requires a change in spin states, and quantum mechanics indicates that such a transition is not favored.
  • phosphorescence generally occurs in a time frame exceeding at least 10 nanoseconds, and typically greater than 100 nanoseconds. If the natural radiative lifetime of phosphorescence is too long, triplets may decay by a non-radiative mechanism, such that no light is emitted.
  • Organic phosphorescence is also often observed in molecules containing heteroatoms with unshared pairs of electrons at very low temperatures. 2,2'-bipyridine is such a molecule.
  • Non-radiative decay mechanisms are typically temperature dependent, such that an organic material that exhibits phosphorescence at liquid nitrogen temperatures typically does not exhibit phosphorescence at room temperature. But, as demonstrated by Baldo, this problem may be addressed by selecting phosphorescent compounds that do phosphoresce at room temperature.
  • Representative emissive layers include doped or un- doped phosphorescent organometallic materials such as disclosed in U.S. Patent Nos. 6,303,238; 6,310,360; 6,830,828; and 6,835,469; U.S. Patent Application Publication Nos. [0112]
  • the excitons in an OLED are believed to be created in a ratio of about 3:1, i.e., approximately 75% triplets and 25% singlets.
  • Phosphorescence may be preceded by a transition from a triplet excited state to an intermediate non-triplet state from which the emissive decay occurs.
  • organic molecules coordinated to lanthanide elements often phosphoresce from excited states localized on the lanthanide metal.
  • such materials do not phosphoresce directly from a triplet excited state but instead emit from an atomic excited state centered on the lanthanide metal ion.
  • the europium diketonate complexes illustrate one group of these types of species.
  • Phosphorescence from triplets can be enhanced over fluorescence by confining, preferably through bonding, the organic molecule in close proximity to an atom of high atomic number. This phenomenon, called the heavy atom effect, is created by a mechanism known as spin-orbit coupling. Such a phosphorescent transition may be observed from an excited metal-to-ligand charge transfer (MLCT) state of an organometallic molecule such as tris(2-phenylpyridine)iridium(III).
  • MLCT excited metal-to-ligand charge transfer
  • triplet energy refers to an energy corresponding to the highest energy feature discernable in the phosphorescence spectrum of a given material.
  • the highest energy feature is not necessarily the peak having the greatest intensity in the phosphorescence spectrum, and could, for example, be a local maximum of a clear shoulder on the high energy side of such a peak.
  • organometallic refers to compounds which have an organic group bonded to a metal through a carbon-metal bond. This class does not include per se coordination compounds, which are substances having only donor bonds from heteroatoms, such as metal complexes of amines, halides, pseudohalides (CN, etc.), and the like. In practice organometallic compounds generally comprise, in addition to one or more carbon-metal bonds to an organic species, one or more donor bonds from a heteroatom.
  • the carbon-metal bond to an organic species refers to a direct bond between a metal and a carbon atom of an organic group, such as phenyl, alkyl, alkenyl, etc., but does not refer to a metal bond to an "inorganic carbon,” such as the carbon ofCN or CO.
  • Figure 1 shows an organic light emitting device 100.
  • Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, and a cathode 160.
  • Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164.
  • Device 100 may be fabricated by depositing the layers described, in order.
  • Substrate 110 may be any suitable substrate that provides desired structural properties.
  • Subsfrate 110 may be flexible or rigid.
  • Substrate 110 may be transparent, translucent or opaque.
  • Plastic and glass are examples of preferred rigid substrate materials.
  • Plastic and metal foils are examples of preferred flexible substrate materials.
  • Substrate 110 may be a semiconductor material in order to facilitate the fabrication of circuitry.
  • substrate 110 may be a silicon wafer upon which circuits are fabricated, capable of controlling OLEDs subsequently deposited on the substrate. Other substrates may be used.
  • the material and thickness of substrate 110 may be chosen to obtain desired structural and optical properties.
  • Anode 115 may be any suitable anode that is sufficiently conductive to transport holes to the organic layers.
  • the material of anode 115 preferably has a work function higher than about 4 eV (a "high work function material").
  • Preferred anode materials include conductive metal oxides, such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AlZnO), and metals.
  • Anode 115 (and substrate 110) may be sufficiently transparent to create a bottom-emitting device.
  • a preferred transparent substrate and anode combination is commercially available ITO (anode) deposited on glass or plastic (substrate).
  • a flexible and transparent substrate-anode combination is disclosed in United States Patent Nos.
  • Anode 115 may be opaque and / or reflective. A reflective anode 115 may be preferred for some top-emitting devices, to increase the amount of light emitted from the top of the device.
  • the material and thickness of anode 115 may be chosen to obtain desired conductive and optical properties. Where anode 115 is transparent, there may be a range of thickness for a particular material that is thick enough to provide the desired conductivity, yet thin enough to provide the desired degree of transparency. Other anode materials and structures may be used.
  • Hole transport layer 125 may include a material capable of transporting holes.
  • Hole transport layer 130 may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity.
  • ⁇ -NPD and TPD are examples of intrinsic hole transport layers.
  • An example of a p-doped hole transport layer is m-MTDATA doped with F 4 -TCNQ at a molar ratio of 50:1, as disclosed in United States Patent Application Publication No. 2003-0230980 to Forrest et al., which is incorporated by reference in its entirety. Other hole transport layers may be used.
  • Emissive layer 135 may include an organic material capable of emitting light when a current is passed between anode 115 and cathode 160.
  • emissive layer 135 contains a phosphorescent emissive material, although fluorescent emissive materials may also be used. Phosphorescent materials are preferred because of the higher luminescent efficiencies associated with such materials.
  • Emissive layer 135 may also comprise a host material capable of transporting electrons and / or holes, doped with an emissive material that may trap electrons, holes, and / or excitons, such that excitons relax from the emissive material via a photoemissive mechanism.
  • Emissive layer 135 may comprise a single material that combines transport and emissive properties.
  • emissive layer 135 may comprise other materials, such as dopants that tune the emission of the emissive material.
  • Emissive layer 135 may include a plurality of emissive materials capable of, in combination, emitting a desired spectrum of light. Examples of phosphorescent emissive materials include Ir( ⁇ py) 3 . Examples of fluorescent emissive materials include DCM and DMQA. Examples of host materials include Alq 3 , CBP and mCP. Examples of emissive and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety.
  • Emissive material may be included in emissive layer 135 in a number of ways.
  • an emissive small molecule may be incorporated into a polymer. This may be accomplished by several ways: by doping the small molecule into the polymer either as a separate and distinct molecular species; or by incorporating the small molecule into the backbone of the polymer, so as to form a co-polymer; or by bonding the small molecule as a pendant group on the polymer.
  • Other emissive layer materials and structures may be used.
  • a small molecule emissive material may be present as the core of a dendrimer.
  • Many useful emissive materials include one or more ligands bound to a metal center.
  • a ligand may be referred to as "photoactive” if it contributes directly to the luminescent properties of an organometallic emissive material.
  • a "photoactive" ligand may provide, in conjunction with a metal, the energy levels from which and to which an electron moves when a photon is emitted.
  • Other ligands may be referred to as "ancillary.”
  • Ancillary ligands may modify the photoactive properties of the molecule, for example by shifting the energy levels of a photoactive ligand, but ancillary ligands do not directly provide the energy levels involved in light emission.
  • a ligand that is photoactive in one molecule may be ancillary in another.
  • Electron transport layer 145 may include a material capable of transporting electrons. Electron transport layer 145 may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Alq 3 is an example of an intrinsic electron transport layer. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1 :1, as disclosed in United States Patent Application Publication No. 2003-0230980 to Forrest et al., which is incorporated by reference in its entirety. Other electron transport layers may be used.
  • the charge carrying component of the electron transport layer may be selected such that electrons can be efficiently injected from the cathode into the LUMO (Lowest Unoccupied Molecular Orbital) energy level of the electron transport layer.
  • the "charge carrying component” is the material responsible for the LUMO energy level that actually transports electrons. This component may be the base material, or it may be a dopant.
  • the LUMO energy level of an organic material may be generally characterized by the electron affinity of that material and the relative electron injection efficiency of a cathode may be generally characterized in terms of the work function of the cathode material.
  • the preferred properties of an electron transport layer and the adjacent cathode may be specified in terms of the electron affinity of the charge carrying component of the ETL and the work function of the cathode material.
  • the work function of the cathode material is preferably not greater than the electron affinity of the charge carrying component of the electron transport layer by more than about 0.75 eV, more preferably, by not more than about 0.5 eV. Similar considerations apply to any layer into which electrons are being injected.
  • Cathode 160 may be any suitable material or combination of materials known to the art, such that cathode 160 is capable of conducting electrons and injecting them into the organic layers of device 100. Cathode 160 may be transparent or opaque, and may be reflective. Metals and metal oxides are examples of suitable cathode materials. Cathode 160 may be a single layer, or may have a compound structure. Figure 1 shows a compound cathode 160 having a thin metal layer 162 and a thicker conductive metal oxide layer 164. In a compound cathode, preferred materials for the thicker layer 164 include ITO, IZO, and other materials known to the art. U.S. Patent Nos.
  • cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer.
  • the part of cathode 160 that is in contact with the underlying organic layer, whether it is a single layer cathode 160, the thin metal layer 162 of a compound cathode, or some other part, is preferably made of a material having a work function lower than about 4 eV (a "low work function material").
  • Other cathode materials and structures may be used.
  • An electron blocking layer 130 may be disposed between emissive layer 135 and the hole transport layer 125, to block elecfrons from leaving emissive layer 135 in the direction of hole transport layer 125.
  • a hole blocking layer 140 may be disposed between emissive layerl35 and electron transport layer 145, to block holes from leaving emissive layer 135 in the direction of electron transport layer 145. Blocking layers may also be used to block excitons from diffusing out of the emissive layer.
  • the theory and use of blocking layers is described in more detail in United States Patent No. 6,097,147 and United States Patent Application Publication No. 2003-0230980 to Forrest et al., which are incorporated by reference in their entireties.
  • blocking layer means that the layer provides a barrier that significantly inhibits transport of charge carriers and/or excitons through the device, without suggesting that the layer necessarily completely blocks the charge carriers and/or excitons.
  • the presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer.
  • a blocking layer may be used to confine emission to a desired region of an OLED.
  • injection layers are comprised of a material that may improve the injection of charge carriers from one layer, such as an electrode or an organic layer, into an adjacent organic layer. Injection layers may also perform a charge transport function.
  • hole injection layer 120 may be any layer that improves the injection of holes from anode 115 into hole transport layer 125.
  • CuPc is an example of a material that may be used as a hole injection layer from an ITO anode 115, and other anodes.
  • electron injection layer 150 may be any layer that improves the injection of electrons into electron transport layer 145.
  • LiF / Al is an example of a material that may be used as an electron injection layer into an electron transport layer from an adjacent layer.
  • a hole injection layer may comprise a solution deposited material, such as a spin-coated polymer, e.g., PEDOT:PSS, or it may be a vapor deposited small molecule material, e.g., CuPc or MTDATA.
  • a solution deposited material such as a spin-coated polymer, e.g., PEDOT:PSS, or it may be a vapor deposited small molecule material, e.g., CuPc or MTDATA.
  • a hole injection layer may planarize or wet the anode surface so as to provide efficient hole injection from the anode into the hole injecting material.
  • a hole injection layer may also have a charge carrying component having HOMO (Highest Occupied Molecular Orbital) energy levels that favorably match up, as defined by their herein-described relative ionization potential (IP) energies, with the adjacent anode layer on one side of the HIL and the hole transporting layer on the opposite side of the HIL.
  • the "charge carrying component” is the material responsible for the HOMO energy level that actually transports holes. This component may be the base material of the HIL, or it may be a dopant.
  • a doped HIL allows the dopant to be selected for its electrical properties, and the host to be selected for morphological properties such as wetting, flexibility, toughness, etc.
  • Preferred properties for the HIL material are such that holes can be efficiently injected from the anode into the HIL material.
  • the charge carrying component of the HIL preferably has an IP not more than about 0.7 eV greater that the IP of the anode material. More preferably, the charge carrying component has an IP not more than about 0.5 eV greater than the anode material. Similar considerations apply to any layer into which holes are being injected.
  • HIL materials are further distinguished from conventional hole transporting materials that are typically used in the hole transporting layer of an OLED in that such HIL materials may have a hole conductivity that is substantially less than the hole conductivity of conventional hole transporting materials.
  • the thickness of the HIL of the present invention may be thick enough to help planarize or wet the surface of the anode layer. For example, an HIL thickness of as little as 10 nm may be acceptable for a very smooth anode surface. However, since anode surfaces tend to be very rough, a thickness for the HIL of up to 50 nm may be desired in some cases.
  • a protective layer may be used to protect underlying layers during subsequent fabrication processes.
  • the processes used to fabricate metal or metal oxide top electrodes may damage organic layers, and a protective layer may be used to reduce or eliminate such damage.
  • protective layer 155 may reduce damage to underlying organic layers during the fabrication of cathode 160.
  • a protective layer has a high carrier mobility for the type of carrier that it transports (electrons in device 100), such that it does not significantly increase the operating voltage of device 100.
  • CuPc, BCP, and various metal phthalocyanines are examples of materials that may be used in protective layers. Other materials or combinations of materials may be used.
  • protective layer 155 is preferably thick enough that there is little or no damage to underlying layers due to fabrication processes that occur after organic protective layer 160 is deposited, yet not so thick as to significantly increase the operating voltage of device 100.
  • Protective layer 155 may be doped to increase its conductivity.
  • a CuPc or BCP protective layer 160 may be doped with Li.
  • Figure 2 shows an inverted OLED 200.
  • the device includes a substrate 210, an cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230.
  • Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200.
  • Figure 2 provides one example of how some layers may be omitted from the structure of device 100.
  • hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer.
  • an OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to Figures 1 and 2.
  • OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190, Friend et al., which is incorporated by reference in its entirety.
  • PLEDs polymeric materials
  • OLEDs having a single organic layer may be- used.
  • OLEDs may be stacked, for example as described in U.S. Patent No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety.
  • the OLED structure may deviate from the simple layered structure illustrated in Figures 1 and 2.
  • the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Patent No.
  • any of the layers of the various embodiments may be deposited by any suitable method.
  • preferred methods include thermal evaporation, ink-jet, such as described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Patent No.
  • OVPD organic vapor phase deposition
  • deposition by organic vapor jet printing such as described in U.S. Patent Application No. 10/233,470, which is incorporated by reference in its entirety.
  • OJP organic vapor jet printing
  • Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere.
  • preferred methods include thermal evaporation.
  • Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Patent Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink- jet and OVJD.
  • the materials to be deposited may be modified to make them compatible with a particular deposition method.
  • substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
  • substituents may be added to a compound having three bidentate ligands, such that after the substituents are added, one or more of the bidentate ligands are linked together to form, for example, a tetradentate or hexadentate ligand. Other such linkages may be formed. It is believed that this type of linking may increase stability relative to a similar compound without linking, due to what is generally understood in the art as a "chelating effect.”
  • Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, lights for interior or exterior illumination and / or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a large area wall, theater or stadium screen, or a sign.
  • PDAs personal digital assistants
  • Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix.
  • the materials and structures described herein may have applications in devices other than OLEDs.
  • other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures.
  • organic devices such as organic transistors, may employ the materials and structures.
  • the term "carbene” refers to compounds having a divalent carbon atom with only six electrons in its valence shell when not coordinated to a metal.
  • a useful exercise to determine whether a ligand includes a carbene-metal bond is to mentally deconstruct the complex as a metal fragment and a ligand, and to then determine whether a carbon atom in the ligand that was previously bound to the metal is a neutral divalent carbon atom in the deconstructed state.
  • the resonance forms of a preferred embodiment may be shown as:
  • Such structures that use an arrow to represent the presence of a metal-carbene bond are used interchangeably herein with structures that do not include the arrow, without any intention of suggesting there is a difference in the structure shown.
  • This definition of carbene is not limited to metal-carbene complexes synthesized from carbenes, but is rather intended to address the orbital structure and electron distribution associated with the carbon atom that is bound to the metal. The definition recognizes that the "carbene” may not technically be divalent when bound to the metal, but it would be divalent if it were detached from the metal.
  • a compound comprising a carbene ligand bound to a metal center is provided.
  • Carbene compounds include small molecules, dendrimers, and polymers that include a carbene-metal bond.
  • the compound is a phosphorescent emissive material, preferably a dopant.
  • the compound may also be doped into a wide band gap host material such as disclosed in U.S. Pat. Application No. 10/680,066, which is incorporated by reference in its entirety, or it may be doped into an inert wide band gap host such as disclosed in WO-074015, which is incorporated by reference in its entirety.
  • Embodiments of the present invention include metal-carbene compounds as high energy host materials. Such materials may be most useful for doped blue and green devices.
  • the dopant in this case could be a triplet emitter or a singlet emitter (using phosphor sensitized fluorescence).
  • the dopant is a blue or UV emissive material.
  • the host material preferably has a wide energy gap.
  • the energy gap refers to the difference in the energy between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) for a particular compound.
  • the triplet energy for a given material is related to, but less than, the energy gap.
  • Materials for use as a wide gap host are selected to have a wide energy gap so that the host material does not quench the dopant emission by endothermic or exothermic energy transfer.
  • the wide gap host is preferably selected so as to have a triplet energy at least about 300 mV higher than that of the dopant.
  • the high band gap of metal-carbene compounds may make these materials effective in carrier blocking and transporting layers. Specifically, these materials may be used in the electron blocking layer, hole blocking layer, exciton blocking layer, hole transport layer, or electron transport layer of an OLED. In other embodiments a metal- carbene compound may be used as a hole injection layer, electron injection layer, or protective layer.
  • metal-carbene compounds described herein have improved thermal stability when incorporated into an organic light emitting device due to the carbene-metal bond, as compared to existing compounds without a carbene-metal bond.
  • Carbene ligands are especially desirable in OLED applications due to the high thermal stability exhibited by metal-carbene complexes. It is believed that the carbene, which behaves much as an electron donative group, generally bonds strongly to the metals, thus forming a more thermally stable complex than, for example, previous cyclometallated complexes used as phosphorescent emitters. It is also believed that carbene analogs of ligands employed in existing phosphorescent emissive materials (for example the phenylpyridine or Irppy, etc.) may exhibit greater stability and emit at substantially higher energy than their existing analogs.
  • a "non-carbene analog" of a metal carbene compound refers to existing ligands having a substantially similar chemical structure to the metal-carbene compound, but unlike the carbene compounds of the present invention, which features a carbene-metal bond, the analog has some other bond, such as a carbon-metal or a nitrogen- metal bond, in place of the carbene-metal bond.
  • Ir(ppz) 3 has a nitrogen in each ligand bound to the Ir.
  • Ir(l-phenylimidazolin-2-ylidene) is analogous to Ir(ppz) 3 where the nitrogen bound to the Ir has been replaced with a carbene bound to the Ir, and where the atoms surrounding the carbene have been changed to make the carbon a carbene.
  • embodiments of the present invention include metal-carbene complexes (e.g. Ir(l- phenylimidazolin-2-ylidene) with similar structures to existing emissive compounds (e.g. Ir(ppz) 3 ).
  • Examples of existing emissive compounds include Ir(ppy) 3 and Ir(ppz) 3 , discussed above. Other examples are disclosed in the references below, which are incorporated herein by reference in their entirety.
  • the carbene ligands are imidazoles, pyrazoles, benzimidazoles, and pyrroles.
  • Metal-carbene complexes may be tuned to emit a wide variety of spectra from the near-ultraviolet across the entire visible spectra by the selection of substituents and/or chemical groups on the ligand(s). More significantly, it may now be possible to obtain saturated blue color emissions with peak wavelengths at about 450 nm. Because it is believed to be materially easier to reduce than to increase the triplet energy by tuning an emissive compound, the ability to make stable blue emitters at such high energies would also allow for the possibility of obtaining any color by reducing the energy so as to red-shift the emission. For example, Fig.
  • FIG. 18 shows that Ir(l-Ph-3-Me-imid) 3 , which is a preferred embodiment of this invention, in a 2-MeTHF solution emits in the near-UV spectra at a wavelength of about 380 nm at 77 K and at room temperature.
  • Fig. 26 shows Ir-(FlMeImid) 3 , which is another embodiment of this invention, to emit at the visible part of the spectra at a wavelength of 462 nm at 77 K and at 466 nm at room temperature.
  • Fig. 21 shows the emission spectra of fac-Ir(l-Ph-3- Me-imid) 3 in 2-MeTHF.
  • the compound exhibits a lifetime of 6.8 ⁇ s at 77 K and 0.50 ⁇ s at room temperature, and the difference may be attributed to quenching mechanisms. It is believed that appropriate substituents on the carbene ligand, or doping in a more rigid matrix, such as disclosed in Turro, "Modern Molecular Photochemistry", University Science Books (1991), 109-10, may increase quantum efficiency at room temperature and correspondingly show longer lifetimes.
  • the emission of a carbene analog may be substantially different from that of its non-carbene analog, and the emission of the carbene analog may be stable and at a higher energy than previously obtainable with stable non-carbene compounds.
  • Embodiments of the present invention shown in Figs. 18, 21, 25, and 26, show higher energy emissions than have previously been obtained with other phosphorescent organometallic emissive materials. It is believed that devices incorporating these materials, and having optimized architecture, will have electroluminescent spectras showing high triplet energies similar to the photoluminescent spectras shown in these figures.
  • the triplet energy of the carbene complex has a corresponding wavelength in the deep blue or ultraviolet (UV) part of the spectra.
  • the phosphorescent emissive compound has triplet energy corresponding to a wavelength of less than 450 nm.
  • the triplet energy corresponds to a wavelength of less than 440 nm, and in even more preferred embodiments, it corresponds to a wavelength less than 400 nm, which is believed to be in the UV region of the spectrum, since 400 nm is believed to represent the cut-off between the UV and the visible regions of the spectrum.
  • Such high triplet energy may make these compounds useful in optically pumping down converting layers.
  • an overlap is preferred between the emission spectra of the ultraviolet carbene compound and the absorption spectra of the down converting layer. It is believed that when about 50 % of the integral of the curve for the normalized electroluminescent spectra of the device is at a wavelength less than about 450 nm, there is sufficient energy to optically pump a down converting layer. More preferably, greater than 90 % of the emission may be produced below 440 nm, as disclosed herein. Preferably, 50 % of the integral of the curve for the normalized electroluminescent spectra is less than about 440 nm, and more preferably, it is less than about 400 nm.
  • the wavelength cutoffs mentioned above are not intended to be absolute limitations as they depend on the energy of the material to be pumped. It is also believed that these emissions may occur at room temperature.
  • the strong metal-carbon bond is also believed to lead to greater spin-orbit coupling in metal carbene complexes.
  • the triplet energy of coordinated carbenes are shown to be significantly higher than pyridine analogs.
  • Fig. 18 shows the emission spectra of mer-Ir(l-Ph-3-Me-imid) 3 , which is one of the embodiments of the invention. The emission is shown to be in the near-ultraviolet range of the spectrum even at room temperature. It is believed herein that other metal carbene complexes may be capable of emitting at similarly high energies due to the strong metal-ligand bond associated with carbene ligands.
  • the stability of metal-carbene complexes may also allow increased versatility in the types of ligands and metals that may be used as phosphorescent emitters in OLEDs.
  • the strong metal- carbene bond may allow a variety of metals to form useful phosphorescent complexes with carbene ligands to give novel emissive compounds.
  • one embodiment includes gold or copper bonded to a carbene ligand.
  • Such metals have been calculated to form metal-carbon bonds having quite high bond dissociation energies, such as illustrated in Nemcsok et al., "The Significance of ⁇ -Interactions in Group 11 Complexes with N-Heterocyclic Carbenes " xxxx American Chemical Society, Publ. on Web, 06/19/2004.
  • metal-carbene complexes may be also used advantageously, because of their improved chemical stability, for other functions in an OLED, for example, as a host material in the emissive layer, as an electron or hole transporting material in an electron or hole transporting layer, and/or as an electron or hole blocking material in an electron or hole blocking layer.
  • cyclometallated complexes are preferred embodiments, the present invention is not limited to such embodiments.
  • the increased strength of a metal- carbene bond, as compared to other types of bonds with metal, may make monodentate ligands feasible for use as emissive materials.
  • bidentate ligands were sfrongly preferred due to stability concerns.
  • embodiments include monodentate carbene ligands as well as bidentate.
  • embodiments also include tridentate carbene ligands, which may be quite stable, and many examples are found in the art, such as those disclosed in Koizumi et al., Organometallics 2003, 22, 970-975.
  • inventions may also feature a tetradentate ligand, such as porphyrin analogs in which one or more nitrogens are replaced by a carbene, which is disclosed in Bourissou et al. Chem Rev. 2000, 100, 39-91.
  • Still other embodiments may include metallaquinone carbenes, which are compounds in which one of the oxygen atoms of a quinone has been replaced by a metal, such as those disclosed in Ashekenazi et al., J. Am. Chem. Soc. 2000, 122, 8797-8798.
  • the metal-carbene compound maybe present as part of a multi-dentate group such as disclosed in U.S. Pat. Application No.
  • the substituents on the carbene-bonded branch of the (C,C)-ligand and the substituents on the mono-anionic-carbon-bonded branch of the (C,C)-ligand may be independently selected from the group consisting of (a) the substituents on the N-bonded branch of the existing (C,N)-ligands, such as disclosed in the references listed below, which is typically but not necessarily a pyridine group; and (b) the substituents on the mono-anionic-carbon-bonded branch of the existing (C,N)-ligands, such as disclosed in the references listed below, which is typically but not necessarily a phenyl group; (c) and/or a combination thereof; and (2) the compounds including the metal-carbene bonds may further include ancillary ligands selected from the group consisting of the ancillary ligands such as disclosed in the following references:
  • Carbene ligands may be synthesized using methods known in the art, such as those disclosed in Cattoen, et al., J. Am. Chem. Soc, 2004, 126; 1342-1343; Chiu-Yuen Wong, et al, Organometallics 2004, 23, 2263-2272; Klapars, et al, J. Am. Chem. Soc, 2001, 123; 7727-7729; Bourissou et al. Chem Rev.
  • a phosphorescent emissive compound having the following formula is provided: z 2 X - wherein Z and Z may be a carbon containing moiety, an amine containing moiety, oxygen containing moiety, a phosphine containing moiety, and a sulfur containing moiety.
  • the compound has the structure:
  • M is a metal; the dotted lines represent optional double bonds; each Zi, A, and A' is independently selected from C, N, O, P, or S;
  • Ri, R 2 , and R 3 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl,
  • each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl;
  • (X-Y) is selected from a photoactive ligand or an ancillary ligand, ⁇ is O, 1, or 2.
  • m is a value from 1 to the maximum number of ligands that may be attached to the metal;
  • m + n is the maximum number of ligands that may be attached to metal M.
  • halo or halogen as used herein includes fluorine, chlorine, bromine and iodine.
  • alkyl as used herein contemplates both straight and branched chain alkyl radicals.
  • Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Additionally, the alkyl group may be optionally substituted with one or more substituents selected from halo, CN, CO 2 R, C(O)R, NR 2 , cyclic-amino, NO 2 , and OR, wherein each R is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl.
  • cycloalkyl as used herein contemplates cyclic alkyl radicals.
  • Preferred cycloalkyl groups are those containing 3 to 7 carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, and the like. Additionally, the cycloalkyl group may be optionally substituted with one or more substituents selected from halo, CN, CO 2 R, C(O)R, NR 2 , cyclic-amino, NO 2 , and OR.
  • alkenyl as used herein contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl group may be optionally substituted with one or more substituents selected from halo, CN, CO 2 R, C(O)R, NR 2 , cyclic-amino, NO 2 , and OR. [0164]
  • alkynyl as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkyl groups are those containing two to fifteen carbon atoms.
  • alkynyl group may be optionally substituted with one or more substituents selected from halo, CN, CO 2 R, C(O)R, NR 2 , cyclic-amino, NO 2 , and OR.
  • substituents selected from halo, CN, CO 2 R, C(O)R, NR 2 , cyclic-amino, NO 2 , and OR.
  • aralkyl as used herein contemplates an alkyl group that has as a substituent an aromatic group. Additionally, the aralkyl group may be optionally substituted on the aryl with one or more substituents selected from halo, CN, CO 2 R, C(O)R, NR 2 , cyclic-amino, NO 2 , and OR.
  • heterocyclic group contemplates non- aromatic cyclic radicals.
  • Preferred heterocyclic groups are those containing 3 or 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperdino, pyrrolidino, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like.
  • the heterocyclic group may be optionally substituted with one or more substituents selected from halo, CN, CO R, C(O)R, NR 2 , cyclic- amino, NO 2 , and OR,
  • aryl or "aromatic group” as used herein contemplates single-ring groups and polycyclic ring systems.
  • the polycyclic rings may have two or more rings in which two carbons are common by two adjoining rings (the rings are "fused") wherein at least one of the rings is aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles and/or heteroaryls.
  • the aryl group may be optionally substituted with one or more substituents selected from halo, CN, CO 2 R, C(O)R, NR 2 , cyclic-amino, NO 2 , and OR,
  • heteroaryl as used herein contemplates single-ring hetero- aromatic groups that may include from one to three heteroatoms, for example, pyrrole, furan, thiophene, imidazoie, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine and pyrimidine, and the like.
  • heteroaryl also includes polycyclic hetero-aromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings are "fused") wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles and/or heteroaryls. Additionally, the heteroaryl group may be optionally substituted with one or more substituents selected from halo, CN, CO 2 R, C(O)R, NR 2 , cyclic-amino, NO 2 , and OR.
  • Embodiments include photoactive carbene ligands.
  • m represents the number of photoactive ligands.
  • m may be 1, 2 or 3.
  • n the number of "ancillary" ligands of a particular type, may be any integer from zero to one less than the maximum number of ligands that may be attached to the metal.
  • (X-Y) represents an ancillary ligand.
  • n may be 0, 1 or 2 for bidentate ligands.
  • Ancillary ligands for use in the emissive material may be selected from those known in the art.
  • Non-limiting examples of ancillary ligands may be found in PCT Application Publication WO 02/15645 Al to Lamansky et al. at pages 89-90, which is incorporated herein by reference.
  • the metal forming the metal-carbene bond may be selected from a wide range of metals. Preferred metals include main group metals, 1 st row transition metals, 2 n row transition metals, 3 rd row transition metals, and lanthanides. Although one skilled in the art typically expects room temperature phosphorescence only from metal atoms that exert a strong heavy atom effect, phosphorescent emission has been observed in Kunkley, et al. J. Organometallic Chem.
  • embodiments also include first row transition metal, such as Ni, and other metals that do not normally exert a strong heavy atom effect but exhibits phosphorescent emission when coordinated to one or more carbene ligands. More preferred metals include 3 r row transition metals. The following are also preferred metals: Ir, Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag. Most preferably, the metal is Iridium.
  • the most preferred embodiments are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N-heterocyclic carbenes, which are N
  • the metal-carbene compound has the structure
  • the ligand has the structure in which i is either an aromatic or an amine group; and R 3 and R 4 together from independently a 5 or 6-member cyclic group, which may be cycloalkyl, cycloheteroalkyl, aryl or heteroaryl, and which may optionally be substituted by one or more substituents J.
  • the metal-carbene compound may have one of the following structures
  • the ligand has the corresponding structure selected from:
  • R 5 and R 6 may be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 C(O)OR', C(O)R', C(O)NR' 2 , NR' 2 , NO 2 , OR', SR', SO 2 , SOR', SO 3 R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; and additionally or alternatively, one or more of Ri and R 2 , R 2 and R 3 , R 3 and R 5 , and R 5 and R 6 together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and
  • the metal carbene compound has the structure:
  • R 8 , R , R 10 , and R ⁇ may be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3
  • each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl;and additionally or alternatively, one or more of Ri and R 2 , R 2 and R 8 , R 8 and R 10 , and R 6 and R 10 together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J.
  • the carbene-metal compound may have one of the structures below:
  • each R 12 maybe hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 C(O)OR', C(O)R', C(O)NR' 2 , NR' 2 , NO 2 , OR', SR', SO 2 , SOR', SO 3 R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R 1 groups on adjacent ring atoms may form a fused 5- or 6-membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally
  • R 13 may be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 C(O)OR', C(O)R', C(O)NR' 2 , NR' 2 , NO 2 , OR', SR', SO 2 , SOR', SO 3 R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' may be halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R 13 groups on adjacent ring atoms may form a fused 5- or 6-membered cyclic group, in which the cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and which is optionally substituted by one or more substituents J; and
  • Z 3 is independently selected from the group consisting of a C, O, S, P, or NR';
  • ring B is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M, wherein ring B can be optionally substituted with one or more substituents R 14 ;
  • ring D is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M, wherein ring D can be optionally substituted with one or more substituents R 15 ; and
  • R 14 and R 15 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 C(O)OR', C(O)R', C(O)NR' 2 , NR' 2 , NO 2 , OR', SiR', SR', SO 2 , SOR', SO 3 R',
  • the metal-carbene has a structure:
  • Another preferred embodiment has the structure:
  • ligand has the structure in which R 6 is an alkyl or aryl group.
  • the metal is Ir.
  • m is 3 and n is 0.
  • R 6 is methyl.
  • n is one.
  • the ancillary ligand X-Y may have one of the following structures:
  • ancillary ligands are acetylacetonate, picolinate, and their derivatives.
  • the carbene compound includes a triazole ring coordinated to a metal.
  • the compound has the structure:
  • the ligands may have the
  • the metal-carbene compound has the structure:
  • carbene ligand has the structure ]
  • Other preferred embodiments include:
  • triazole carbene compound has the structure:
  • the triazole carbene compound has the structure:
  • the carbene compound includes a tefrazole ring coordinated to a metal.
  • the compound has the structure:
  • the compound has the structure:
  • the compound has the structure
  • the compound has the structure: and the ligand has wherein Z 4 and Z 5 are independently selected from a bond, O, S, or NR'; Z ls A, A 1? A', and
  • A" is independently selected from C, N, or P;
  • More preferred embodiments include compounds with the structure:
  • ligands with carbon donors can only be drawn with a zwitterionic resonance structure, and are hereinafter referred to as "zwitterionic carbon donors.” It is possible to draw a resonance structure where the carbon coordinated to the metal center is a carbene as shown below.
  • Preferred compounds having zwitterionic carbon donor ligands include heterocyclic compounds comprising at least one nitrogen atom.
  • Preferred compounds include:
  • Embodiments also include zwitterionic carbon donor ligands with the structure:
  • the carbon coordinated to the metal center is not directly bonded to a heteroatom.
  • Dopant A and B are UV emitters in solution photoluminescence (PL) and the electroluminescence (EL) emission has a highest energy peak or shoulder at about 400 nm as shown in Figure 47.
  • Dopants M, N, O, and P, in Examples 43, 44, 45 and 46 respectively have slightly lower triplet energy and emit in a device with high efficiency using the wide band gap (high triplet energy) host, UGH5. These examples have similar triplet energy and the EL emission shows vibronic fine structure characteristic of the dopant.
  • the emission from these examples is a desirable blue color with a CIE coordinate of about (0.14, 0.15).
  • Other embodiments also include compounds having ancillary carbene ligands.
  • the dopant in the device of Examples 13 and 14 is an Iridium compound having two photoactive phenylpyridine (ppy) ligands and one carbene ancillary ligand:
  • Embodiments also include carbene complexes useful as host materials in
  • the host material comprises a compound having at least one carbene atom coordinated to iridium wherein the compound has the structure:
  • ring A may be an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to iridium, and ring A may be optionally substituted with one or more substituents Ra;
  • R ⁇ may be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group;
  • R 2 -R 5 may be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , CO 2 R', C(O)R', C(O)NR'2, NR'2, NO 2 , OR', SR', SO 2 , SOR', SO 3 R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R or alternatively, two R
  • the corresponding ligand may have the structure:
  • the host material includes a compound having the structure:
  • At least one of Rai and Ra 3 is F. More preferred compounds include:
  • ligands include:
  • the host material comprises a carbene compound having the structure:
  • ring B is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to iridium, wherein ring B may be optionally substituted with one or more substituents Rb;
  • Rb maybe hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , CO 2 R', C(O)R', C(O)NR'2, NR'2, NO 2 , OR', SR', SO 2 , SOR', SO R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two Rb groups on the same ring, together may form independently a 5 or 6-member cyclic group, which may be a cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group may be substituted by one
  • the host material includes a carbene compound having the structure:
  • the host material comprises a carbene compound with the structure:
  • the host materials for the devices of Examples 51-54 comprise Ir(bmi) 3 .
  • the high LUMO energy of the such host material is believed to allow for electron trapping on the dopant, which may lead to efficient charge recombination when holes are confined to the emissive layer.
  • Figure 75 and Figure 78 show that devices that use HPT, which in addition to facilitating electron transport is also effective at blocking holes, exhibit higher quantum efficiency than comparable devices of Example 51 and 53. The higher quantum efficiency may be attributed to efficient recombination that occurs on the dopant and that the host material has a sufficiently high triplet energy to not quench emission from the dopant [0206]
  • the ligand has the structure:
  • the host material comprises a carbene compound with the structure:
  • the carbene ligand has the structure:
  • R and Rai and two adjacent Ra groups on the same ring together form independently a 5 or 6-member cyclic group, which may be a cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group may be substituted by one or more substituents J.
  • More preferred embodiments include carbene compounds having the structure: More preferred carbene ligands include:
  • the host material comprises a carbene compound having the structure:
  • ring C is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to Ir, wherein ring C can be optionally substituted with one or more substituents Re;
  • Re may be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , CO 2 R', C(O)R', C(O)NR'2,
  • the carbene ligand has the structure:
  • the carbene compound has the structure:
  • redox active metal refers to a metal in a complex, i.e., a metal ion surrounded by ligands, that can undergo reduction or oxidation.
  • oxidation and reduction of the complex occur principally at the metal center, and not on the ligands complexed to the metal.
  • the oxidation state of the metal changes upon reduction or oxidation of the complex, such that the electronic density on the ligands remains substantially unchanged, and the ligands, typically, do not dissociate from the complex.
  • the term "redox active reducible metal complex” refers to a metal complex, as described above, where the metal is capable of oxidation and reduction in an electrochemical process.
  • a metal complex of formula TiX ⁇ where X is anionic ligand
  • the Ti is in the 4+ oxidation state, i.e., Ti(IV) or Ti 4+ .
  • an electron is added to the complex, and the complex takes a negative charge, i.e., TiXf, and the Ti is reduced to its 3+ oxidation state, i.e., Ti(III) or Ti 3+ .
  • the electron added in the reduction process is primarily located on the Ti center of the reduced complex.
  • the term "readily switch redox state” refers to a metal complex in a first redox state that can readily switch to a second, accessible redox state at a moderate potential.
  • the redox state of a complex is a function of the number of electrons in the complex, which changes when the complex is reduced or oxidized.
  • oxidation or reduction in a series of single steps adding (reduction) or removing (oxidation) electrons, takes the complex through a series of redox states.
  • the complex gains a negative charge, which increases with each successive reduction. Oxidation of a reduced complex reverses the process.
  • the redox state can be switched readily. If the energy required to shift between redox states is high, the state will not be switched readily.
  • a high kinetic barrier may exist for a change in redox state.
  • the voltage required for the change in state must be accessible in the matrix or solvent containing the complex, and the kinetic barrier to the redox reaction must be a small for the complex to readily switch redox state.
  • the kinetic barriers to electron transfer can be minimized by a careful selection of a metal that has a low reorganization barrier to electron transfer. The kinetic barriers for reduction of metal complexes are best described by Marcus electron transfer theory.
  • the term "resting state” refers to the neutral state of a vacuum deposited device. More generally, the resting state is the redox state of a complex before any charge is injected. For solution processed OLEDs, where the complex is initially in the form of a cation, the cation is the resting state, and the neutral form of the complex carries the elecfron.
  • an OLED in accordance with the invention has at least one organic layer comprising a reversibly reducible metal complex with a redox active metal.
  • This complex may be used in the device at least as an ETL or as a host material.
  • the preferred reversibly reducible metal complexes readily undergo a reversible change of oxidation state, and, thus, may be referred to as reversibly reducible metal complexes. That is, for example, for a reversibly reducible metal complex comprising Ti(IV) as the metal, the Ti(IV) may be reduced to Ti(III) in the complex without the dissociation of a ligand, and then oxidized to Ti(IV). This process allows for the transport of electrons through the material.
  • a preferred OLED of the invention comprises an anode; a cathode; and at least one organic layer disposed between the anode and the cathode.
  • the organic layer comprises a reversibly reducible metal complex of a redox active metal center and at least one ligand, where, following a reduction of the complex that adds one extra electron to the complex, the extra electron is predominantly localized on the metal center of the reduced complex. That is, as will be recognized by those skilled in the art, substantially all of the charge of the electron will be on the metal, rather than on the ligands.
  • the location of the electron in such a reduced complex may be determined with X-Ray Absorption Fine Structure ("XAFS”) techniques, but is best determined through theoretical calculations, such as density function theory calculation (DFT), or Electron Paramagnetic Resonance (“EPR”).
  • XAFS X-Ray Absorption Fine Structure
  • DFT density function theory calculation
  • EPR Electron Paramagnetic Resonance
  • the metal is a d(0) metal, such as Ti(IV).
  • DFT density function theory calculation
  • EPR Electron Paramagnetic Resonance
  • Useful ligands preferably contain two electron donors, such as carbenes, that form a coordinatively saturated metal center, and do not dissociate from the metal center upon reduction of the complex.
  • Carbenes are particularly preferred, as carbenes are less likely to dissociate from the metal complex upon reduction of the complex, due to the strength of the carbene-metal bond.
  • Particularly useful ligands include, but are not limited to:
  • E 1 and E 3 are either/or nitrogen, oxygen, or sulfur mono anionic donors
  • E 2 is a C, N, P, Si, etc neutral donor
  • the reversibly reducible metal complexes useful in the invention are neutral and substantially colorless in the resting state, preferably having an extinction coefficient at wavelengths from about 400nm to about 750 nm in the resting state of no more than about 1000 M ⁇ -cm "1 , and, more preferably, no more than about 100 M ⁇ -cm "1 .
  • Preferred reducible metal complexes in accordance with the invention are of Formula I and Formula II
  • Mi is a redox active transition metal, preferably a redox active dO transition metal
  • E 1 and E 3 are independently selected from nitrogen, oxygen, and sulfur mono-anionic donors
  • E 2 is a C, N, P, or Si neutral donor
  • (X-Y) is selected from a photoactive ligand or an ancillary ligand
  • m is a value from 1 to the maximum number of ligands that maybe attached to metal Mi
  • m + n is the maximum number of ligands that may be attached to metal Mi, such that the overall complex is neutral.
  • Particularly useful reversibly reducible metal complexes include, but are not limited to complexes of formula:
  • E 1 and E 3 are either/or nitrogen, oxygen, or sulfur mono anionic donors, and E is a C, N, P, Si, or similar neutral donor,
  • the metal-carbene complex is cationic.
  • the cationic metal-carbene complex will have as positive charge ranging from 1 + to 6 + , and preferably from 1 to 3 .
  • the cationic metal-carbene complex will be associated with a counterion to balance the charge.
  • the counterion may be selected from any appropriate anion which does not interfere with the function of the compound in the device, for example, as an emissive material.
  • the anion is selected to be electrochemically inert over the operational voltage range of the device.
  • Preferred counteranions are typically weakly coordinating anions.
  • weakly coordinating anion is well known in the art per se and generally refers to a large bulky anion capable of delocalization of the negative change of the anion.
  • the weakly coordinating nature of such anions is known to those skilled in the art and described in the literature (S. Strauss et al., Chem. Rev., 1993, 93, 927).
  • the metal center, the carbene ligand(s), the optional ancillary ligand(s), and the optional additional photoactive ligand(s) are selected in combination so that the resulting metal complex has a positive charge.
  • the cationic metal-carbene complex will be an emissive material.
  • the cationic metal-carbene complex will further comprise one or more carbon-metal bonds that are not carbene-metal bonds (i.e., a covalent carbon-metal bond).
  • a covalent carbon-metal bond particularly preferred is a phenyl bonded to the metal center, as it is believed that this type of bonding promotes relaxation, which may result in better emissive properties.
  • the cationic metal-carbene complex will have at least one carbon-metal bond that is a carbene-metal bond and at least one carbon- metal bond that is a non-carbene carbon-metal bond, and preferably is a phenyl-metal bond.
  • the emissive cationic metal-carbene complex emits in the blue region of the visible spectrum.
  • the emissive cationic metal-carbene complex will preferably have an emission spectra with the ⁇ max less than about 500 nm, and more preferable less than about 450 nm.
  • the device comprising the cationic metal-carbene complex will emit light having CIE coordinates wherein the X-coordinate is from about 0.10 to about 0.15, and the Y-coordinate in from about 0.10 to about 0.20.
  • the embodiments of the cationic metal-carbene complexes will have associated therewith (i) a positive charge, and (ii) an anionic species to provide charge balance. While the structures shown herein do not in many cases have an explicit charge indicated, it is to be understood that the ligands and metals are selected so as to give an overall positive charge for the complex. For example, two monoanionic bidentate carbene ligands plus a third neutral XY ligand chelated to a metal with a +3 oxidation state will result in a positively charged complex. An example of this is shown below where two carbene ligands and one bypyridine ligand chelated to an Ir(III) metal give a complex with an overall charge of +1:
  • the carbene ligands of the cationic metal-carbene complexes are preferably multidentate.
  • the carbene ligand has two to six bonds to the metal center, at least one of which is a carbene-metal bond.
  • the carbene ligands discussed above, for example in tables 38-41 maybe linked by linking groups to other carbene ligands or to ancillary ligands to give tridetate, tetradentate or hexadentate ligand systems. Suitable linking groups include, for example, lower alkyl groups, ethers, alkyl-aryl-alkyl, each of which may be substituted. Additional linking groups are taught in U.S. application serial No.
  • Suitable tridentate ligands are taught in co-pending application Docket No. 10020/33001, which is incorporated herein by reference in its entirety.
  • Suitable tetradentate ligands are taught in co-pending application Docket No. 10020/33201, which is incorporated herein by reference in its entirety.
  • the cationic metal-carbene complexes of the present invention will generally be unsuitable for deposition using vapor deposition methods such as sublimation. Rather, the cationic metal-carbene complexes are preferably deposited using solution-based processing, such as spin coating and ink-jet printing.
  • the carbene ligand may be substituted to affect charge transport.
  • a triarylamine TAA
  • TAA triarylamine
  • This type of substitution may also be designed to trap charges to control recombination in the emissive layer, which may lead to more stable and efficient devices.
  • tripodal ligands such as those shown below.
  • Substituents may include groups that are believed to be emissive or have charge transport properties.
  • carbenes that exhibit improved stability or are easier to synthesize.
  • carbenes that exhibit improved stability or are easier to synthesize.
  • hexadentate carbene complexes which may be linked by a phenyl ring, for example:
  • the organic layer comprises an emissive material having the formula III:
  • M is a second or third row transition metal; the dotted lines represent optional double bonds;
  • L is an ancillary ligand
  • X 1 is selected from C and N;
  • X 2 is selected from C, N, O, S and P;
  • X 3 is selected from C and N; each Q is independently selected from a chemical bond and -C(R') 2 -;
  • Y 2 is C, N, O, S or P, wherein when Y 1 is N, Y 2 is C or N;
  • R 1 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR' 2 , aryl and heteroaryl; a is 1 or 2; R 3 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR' 2 , aryl and heteroaryl; c is 1 or 2; alternatively, R 1 and R 3 , taken together with Y 1 and Y 2 , form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C
  • Z 2 is C, N, O, S or P, wherein when Y 1 is N, Y 2 is C or N;
  • R 2 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR' 2 , aryl and heteroaryl;
  • b is 1 or 2;
  • R 4 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR' 2 , aryl and heteroaryl;
  • d is 1 or 2;
  • 9 4 1 9 alternatively, R and R , taken together with Z and Z form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, a
  • R 5 and R 6 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R',
  • R 5 and R 6 taken together with X 1 , X 2 and X 3 form a 5- or 6- membered cyclic group or a 8- to 10-membered fused' bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', or SO 3 R' halo, aryl and heteroaryl; additionally or alternatively R 1 and R 5 taken together with X 1 , Q and Y 1 form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted
  • M is selected from Ru, Os, Re, Rh, Ir, Pd and Pt.
  • M is selected from Os and Ru, and in still more preferred embodiments, M is Os.
  • Os is the preferred metal as it is relatively easy to oxidize.
  • the emissive material has an oxidation potential that is more positive than about -0.7 volts, more preferably more positive than about -0.3 volts, and still more preferably more positive than about 0 volts, relative to Ferrocene/Fe ⁇ Ocenium cation.
  • X 2 of the compound according to the formula III is selected from C and N.
  • At least one of X 2 , Y 2 or Z 2 is C and is selected to be a carbene donor.
  • the compound according to the formula III is a neutral compound.
  • Neutral compound may have the advantage of being easier to process in the manufacture of the device as they may be deposited using sublimation techniques.
  • the compound according to the formula III will include a counterion to balance the charge.
  • the metal complex will have as positive charge ranging from 1 + to 6 + , and preferably from 1 + to 3 + .
  • the counterion may be selected from any appropriate anion which does not interfere with the function of the compound in the device, for example, as an emissive material.
  • the anion is selected to be electrochemically inert over the operational voltage range of the device.
  • Preferred counteranions are typically weakly coordinating anions.
  • weakly coordinating anion is well known in the art per se and generally refers to a large bulky anion capable of delocalization of the negative change of the anion.
  • the weakly coordinating nature of such anions is known to those skilled in the art and described in the literature (S. Strauss et al., Chem. Rev., 1993, 93, 927).
  • R 5 and R are taken together with X 1 , X 2 and X 3 form a cyclic group (denoted as ring A) to give a compound having the formula IV:
  • M is a second or third row transition metal; the dotted lines represent optional double bonds;
  • L is an ancillary ligand
  • X 1 is selected from C and N;
  • X 2 is selected from C, N, O, S and P;
  • X 3 is selected from C and N; ting A selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, wherein ring A may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', or SO 3 R' halo, aryl and heteroaryl; each Q is independently selected from a chemical bond and -C(R') 2 -;
  • Y 2 is C, N, O, S or P, wherein when Y 1 is N, Y 2 is C or N;
  • R 1 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR' 2 , aryl and heteroaryl; a is 1 or 2;
  • R 3 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR' 2 , aryl and heteroaryl; c is 1 or 2; alternatively, R and R , taken together with Y and Y , form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which maybe optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', or SO 3 R' halo, aryl and heteroaryl; z s C orN;
  • Z 2 is C, N, O, S or P, wherein when Y 1 is N, Y 2 is C or N;
  • R 2 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR' 2 , aryl and heteroaryl; b is 1 or 2;
  • R 4 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR' 2 , aryl and heteroaryl; d is 1 or 2; alternatively, R 2 and R , taken together with Z 1 and Z , form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', or SO 3 R' halo, aryl and heteroaryl; additionally or alternatively R 1 and R 5 taken together with X 1 , Q and Y 1 form a
  • R 1 , R z , R R X 1 , X z , X J , Y 1 , Y , Z 1 , Z , M, ⁇ ngA, Q, a, b, c, and d are as described for a compound of the formula II.
  • Compounds which comprise two tridentate ligands are preferred. Such compounds are preferred as it is believed that such ligand configurations may improve the stability of the materials when incorporated into an organic light emitting device. Further, such materials may have the additional advantage of being more stable to sublimation during preferred deposition techniques such as OVPD.
  • ring A is selected to be a phenyl or pyridyl ring, which ring may be further substituted, to give a compound having the formula VI: wherein
  • M is a second or third row transition metal
  • X 2 is selected from C or N;
  • R 7 , R 8 and R 9 are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 ,
  • R 5 and R 6 or R 6 and R 7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 ,
  • R 1 and R 7 taken together with the atoms to which they are attached form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', or SO 3 R' halo, aryl and heteroaryl; 9 0 additionally or alternatively R and R taken together with the atoms to which they are attached form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-
  • R 1 , R 2 , R 3 , R 4 , Y 1 , Y 2 , Z 1 , Z 2 , M, Q, a, b, c, and d are as described for a compound of the formula IV.
  • R and R are selected to form a ring
  • ring B and ring C are independently selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', or SO 3 R' halo, aryl and heteroaryl, 1 9 1 9 1 and X , X , X , Y , Y , Z , Z , M, L, Q, a, b, c, d, n and m are as described for a compound of the formula IV.
  • ring A is selected to be a phenyl or pyridyl ring, which ring may be further substituted, to give a compound having the formula VIII:
  • X is selected from C or N;
  • ring B and ring C are independently selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', or SO 3 R' halo, aryl and heteroaryl;
  • R 7 , R 8 and R 9 are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 ,
  • X is selected from C or N;
  • ring B and ring C are independently selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', or SO 3 R' halo, aryl and heteroaryl;
  • R , R and R are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2
  • Q is selected to be a linking group such as -C(R') 2 -, rather than a chemical bond.
  • a preferred linking group is -CH 2 -.
  • the inclusion of a linking group may allow the metal- binding sites of the ligand to more closely achieve the preferred coordination geometry of the metal center.
  • M is Os
  • the emissive material has the formula X:
  • M is a second or third row transition metal
  • X 2 is selected from C or N
  • Q is abond or -C(R') 2 -;
  • R 7 , R 8 and R 9 are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', or SO 3 R' halo, aryl and heteroaryl; and additionally or alternatively, R 5 and R 6 or R 6 and R 7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2
  • R is selected from alkyl, aryl and aralkyl
  • R 10 and R 11 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 ,
  • R 10 and R 11 , or R 11 and R 12 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R',
  • R 22 is selected from alkyl, aryl and aralkyl
  • R 20 and R 21 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 ,
  • R 20 and R 21 , or R 21 and R 22 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', or SO 3 R' halo, aryl and heteroaryl; and each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and hetero
  • the emissive material has the formula XI:
  • M is a second or third row transition metal
  • X 2 is selected from C or N;
  • R , R and R are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ,
  • R 5 and R 6 or R 6 and R 7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 ,
  • R is selected from alkyl, aryl and aralkyl
  • R 10 and R 11 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ,
  • R 10 and R 11 , or R 11 and R 12 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR ⁇ C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', or SO 3 R' halo, aryl and heteroaryl;
  • R 22 is selected from alkyl, aryl and aralkyl
  • R 20 and R 21 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 ,
  • R and R , or R and R form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R',
  • each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl.
  • the emissive material has the formula XII:
  • M is a second or third row transition metal
  • Y and Z are independently selected from C and N;
  • R 8 , R 9 , R 13 , R 14 , R 15 , R 16 , R 23 , R 24 , R 25 , and R 26 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 ,
  • R 8 and R 9 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 ,
  • R 13 and R 14 , or R 14 and R 15 , or R 15 and R 16 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', or SO 3 R' halo, aryl and heteroaryl; and additionally or alternatively R 23 and R 24 , or R 24 and R 25 , or R 25 and R 26 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')
  • Preferred substituents off of the aryl and heteroaryl groups include CF 3 , CN,
  • the substituent R 8 of compounds VI, VIII, IX, X and XI is selected from CF , CN, CH , F, and phenyl, with CF 3 and CN being particularly preferred.
  • Preferred embodiments include osmium complexes which comprise two tridentate ligands each of which have a bond to the metal center from a carbenes and from an anionic phenyl ring, such as:
  • osmium complexes which comprise two tridentate ligands, each of which has two carbenes and one anionic phenyl ring, such as:
  • the emissive material is a charged compound, as exemplified below:
  • the emissive material comprises a charged compound
  • the material will have associated with it a counterion to balance the charge.
  • the organic light emitting device may comprise a material, which may be an emissive material, wherein the material comprises two tridentate ligands bound to the metal center through at least one carbon-metal bond, wherein carbon- metal bonds are not carbene-metal bonds, as exemplified below:
  • the emissive materials are macrocyclic electrophosphors.
  • the phosphorescent emissive material comprises a heavy metal atom and a multidentate ligand system, for example a tetradentate or hexadentate ligand system.
  • a multidentate ligand system for example a tetradentate or hexadentate ligand system.
  • the donor atoms are members of a ring. The most stable complexes are formed when the internal diameter of the ring corresponds to the diameter of the cation.
  • linking group In order to form a macrocyclic ligand, two or more ligands are linked to one another by a linking group.
  • the linking group may be connected to each ligand by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the ligand's ability to bind to the metal.
  • Linking groups include, for example, organic, organometallic, and other metal containing groups. Representative groups suitable for use as a linking group are bivalent and trivalent alkyl groups, aryl groups, silanes, ethers, and polyethers.
  • the ligands that are joined by a linking group are directly bonded to one another, in which case the term "linking group" is meant to refer to that bond.
  • two bidentate ligands are linked by a single linking group.
  • two bidentate ligands are linked by two linking groups.
  • the linking groups within the macrocyclic ligand can be the same or different from one another.
  • a tetradentate ligand comprises four linking groups, two of which comprise one or more linking atoms or heteroatoms and two of which are single bonds.
  • the linking group provides no ⁇ -conjugation between the linked ligands. Having ⁇ -conjugation between the linked ligands may change the electronic properties of the ligands and the resulting metal complexes, such as a red-shift in the luminescence. It is desirable to link the ligands together to without significantly altering the electronic properties of the ligands and the resulting metal complex.
  • a non-conjugated linking group may comprise at least one atom in the linkage, which contains no ⁇ -electrons, such as an sp 3 hybridized carbon or silicon.
  • the compound comprising the macrocyclic ligand is organometallic.
  • the ligand is symmetrical across the metal center.
  • Ligand symmetry may contribute to the stability of the macrocyclic ligand system.
  • the ligand is a tetradentate ligand.
  • the tetradentate ligand comprises two identical bidentate ligands, the tetradentate ligand is "square."
  • the tetradentate ligand comprises two 5-membered rings and two 6-membered rings, each ring coordinated to the metal center.
  • the macrocyclic ligand is "planar.”
  • the ligand forms a plane defined by three atoms: two adjacent atoms each coordinated to the metal, and the metal atom itself.
  • the planarity of a ligand can be determined by the angle between planes formed by the atoms coordinated to the metal, i.e., the interplanar angle.
  • the interplanar angle For instance, in formula XVII (described in further detail below), an interplanar angle exists between the plane of the coordinating atoms of W, X, and metal M and the plane of the coordinating atoms of Y, Z, and metal M.
  • an inte ⁇ lanar angle also exists between the plane of W, Z, and M and the plane of X, Y, and M.
  • each interplanar angle is less than about 15°.
  • each interplanar angle is less than about 10°, and most preferably, each interplanar angle is about 0°.
  • the compound of the present invention may be represented by a macrocyclic structure XIII: wherein M is a metal; A is C orN; Zi is C orN; R 1 , R 2 , R 3 , and R 4 are independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, heteroaryl, C(O)R', C(O)OR, or C(O)NR' 2 ; and each of R 1 and R 2 , R 2 and R 3 , and R 3 and R independently and optionally can form a 5- or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently R, O-R', N(R') 2 , SR', C(O)R', C(O)
  • the metal, M is selected from the transition metals having an atomic weight greater than 40.
  • Preferred metals for this embodiment include Ir, Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag. More preferably, the metal is Pt or Pd. Most preferably, the metal is Pt.
  • each substituent J is independently R', O-R', N(R') 2 , SR', C(O)R', C(O)OR', C(O)NR' 2 , CN, CF 3 , NO 2 , SO 2 , SOR', SO 3 R, or halo, wherein any two J groups on adjacent ring atoms can optionally form a 5- or 6-member cyclic group; and wherein each R' is independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, or heteroaryl. Also, the possible cyclic groups formed by adjacent J groups may also be substituted by one or more substituents J.
  • Q is an optional ancillary ligand that may modify the photoactive properties of the molecule, for example by shifting the energy levels of a photoactive ligands, but it does not directly provide the energy levels involved in light emission.
  • the present invention provides a tetradentate compound of structure XIII as described above. This embodiment is depicted as structure XV:
  • two bidentate ligands are linked together by at least one linking group to form a tetradentate.
  • the compounds of the present invention include structures XlVa and XI Vb:
  • Each of structures XlVa and XlVb form a tetradentate when the two bidentate ligands are linked to one another by at least one linking group.
  • the pair of R groups can be linked together, the pair of R 4 groups can be linked together, or both pairs can be linked.
  • structure XlVb one or both of the R 1 groups can be linked to its neighboring R 4 group.
  • the present invention also provides a compound having a structure XV:
  • the present invention provides a compound having a structure XVI:
  • the invention provides an organic light emitting device, comprising an anode, a cathode, and a phosphorescent emissive region disposed between the anode and the cathode, wherein the emissive region comprises an emissive material having the structure XVII: L 1__X L 2 VV M Y
  • W, X, Y, and Z are linked to one another by linking groups
  • L 1 , L 2 , L 3 , and optionally L 4 (x can be 0 or 1).
  • the emissive material has the structure XVIII:
  • M is a metal; the dotted lines represent optional double bonds; W 1 , W 3 , X 1 , X 3 , Y 1 , Y 3 , Z and Z 3 are independently C or N; W 2 , X 2 , Y 2 , and Z 2 are independently C, N, O, S or P; wherein at least one of W 2 , X 2 , Y 2 and Z 2 is a carbene; wherein for each group W, X, Y, and Z at least one of atoms 1, 2, and 3 is C; L 1 , L 2 , and L 3 are independently a linking group; ⁇ R and R may optionally be joined to form a linking group L ; R 1"10 are independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, heteroaryl, C(O)R', C(O)OR*, or C(O)NR' 2 ; each of R 1 and R 2
  • each group W, X, Y, and Z at least one of atoms 1, 2, and 3 is C. That is, at least one of W , W , and W is C. Similarly, at least one of X , X , and X 3 is C. Groups Y and Z are likewise defined.
  • R 7 and R 8 are joined to form a linking group L 4 to give a macrocyclic compound having the structure XIX:
  • R and R (taken together with X 1 , X 2 , and X 3 ) form a cyclic group denoted ring A
  • R 3 and R 4 (taken together with Y 1 , Y 2 , and Y 3 ) form a cyclic group denoted ring B to give a compound having the structure XX: XX wherein A and B are independently a 5- or 6-membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents J.
  • R 5 and R (taken together Q 1 fl 1 9
  • A, B, C, and D are independently a 5- or 6-membered cyclic group or a 8- to 10- membered fused bicyclic group, which may be optionally substituted with one or more substituents J.
  • R 7 and R 8 are joined to form a linking group L to give a compound having the structure XXII:
  • the emissive material is a compound having the structure XXIII:
  • W ⁇ 2 and 1 Zyl are independently C or N;
  • L 2 is a linking group;
  • R ,28 and R ,29 may optionally be joined to form a linking group L ;
  • R ,20-32 are independently a substituent J.
  • L 4 is a linking group
  • the emissive material is a compound having the structure XXV:
  • XXV are neutral compounds.
  • Neutral compound may have the advantage of being easier to process in the manufacture of the device as they may be deposited using sublimation techniques.
  • the compound according to structures XVII- XXV is a charged compound, the compound will include a counterion to balance the charge.
  • the counterion maybe selected from any appropriate ion which does not interfere with the function of the compound as an emissive material.
  • the metal-carbene complex will be cationic. Such complexes will have as positive charge ranging from 1 + to 6 + , and preferably from 1 + to 2 + .
  • the cationic metal-carbene complex will be associated with a weakly coordinating anion to balance the charge.
  • the weakly coordinating anion may be selected from any appropriate anion which does not interfere with the function of the compound in the device, for example, as an emissive material.
  • the weakly coordinating anion is selected to be electrochemically inert over the operational voltage range of the device.
  • the term "weakly coordinating anion" is well known in the art per se and generally refers to a large bulky anion capable of delocalization of the negative change of the anion.
  • the weakly coordinating nature of such anions is known to those skilled in the art and described in the literature (S. Strauss et al., Chem. Rev., 1993, 93, 927).
  • the present invention comprises a compound further comprising one or more carbene atoms coordinated to a d 8 metal.
  • Preferred metals for this embodiment include Pt(II), Pd(II), Ir(I), Au(III), or Rh(I). Most preferably, the metal is Pt(II).
  • the metal is coordinated to one or more carbene donors
  • a donor is a group coordinated to the metal. Each donor may be optionally substituted with one or more substituents J.
  • the donors are linked to form a macrocyclic ligand.
  • the macrocyclic ligand is planar.
  • the metal is coordinated to 4 donors, and the donors are linked to form a tetradentate ligand.
  • the carbene compounds of the present invention are emissive.
  • the metal forms a carbon-metal bond with at least one carbon atom that is not a carbene donor.
  • the metal forms a carbon metal bond with a phenyl group, as it is believed that this type of bonding promotes relaxation, which may result in better emissive properties.
  • the metal is coordinated to two carbene donors and two phenyl groups.
  • the metal is coordinated to two bidentate ligands.
  • the metal is coordinated to one tridentate ligand and one monodentate ligand.
  • the metal is coordinated to a tetradentate ligand.
  • Exemplary carbene donors include, but are not limited to:
  • Exemplary neutral donors include, but are not limited to
  • Exemplary monoanionic donors include, but are not limited to:
  • Preferred carbene compounds of the present invention include:
  • the metal is selected to be a metal that preferably adopts an octahedral coordination sphere (for example, Ir, Os, Rh, Ru, etc.)
  • the axial coordination sites may be occupied by monodentate ancillary ligands.
  • An embodiment of such a compound is provided below:
  • each Q is independently selected from monodentate ancillary ligands.
  • the ligands of the present invention emit blue light, that is, the emission has CIE coordinates in the range that corresponds to saturated blue.
  • Blue emission can be achieved by tuning the ligands. Tuning can be accomplished by altering the size of the pi system and/or adding electron donating or accepting groups.
  • wavelength depends on the line width, one preferred embodiment comprises at least one ligand that has a triplet energy corresponding to a wavelength of less than 450 nm. If a small line width is achieved, for example, 40 nm or less, wavelengths longer than 450 nm would still emit the preferred saturated blue.
  • planar macrocyclic ligands may show aggregation effects at moderate doping levels. This aggregation effect will lead to combined monomer and excimer/dimer emission at intermediate concentrations, and predominate excimer/dimer emission at high concentration. Monomer only emission is expected at low doping levels, but at the cost of lower efficiency.
  • sterically bulky groups may be added to the periphery of the macrocyclic ligands of the present invention. Sterically bulky groups include, but are not limited to, tertiary butyl or mesityl groups. The addition of sterically bulky groups allows for high efficiency OLEDs by allowing emission from the monomer state at high doping levels.
  • L 2 IrL' The process comprises: (a) combining and L' in the presence of an organic solvent form a mixture; (b) maintaining the mixture for sufficient time to obtain I ⁇ IrL'; (c) recovering L 2 IrL' from the mixture, and
  • L is a carbene ligand coordinated to iridium and L' is a bidentate ligand or two monodentate ligands, and L is different from L'.
  • L' may be a carbene or non-carbene ligand.
  • L and L' are both bidentate carbene ligands.
  • L' has a net negative charge and I ⁇ IrL' is a neutral compound. In other embodiments, L' is neutral and I ⁇ IrL' is positively charged.
  • L has the structure
  • A may be C or N;
  • ring B may be an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring, wherein ring B may be optionally substituted with one or more substituents R 3 ;
  • Ri maybe hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group;
  • R 21 , R 22 , and R 3 may each independently be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , CO 2 R', C(O)R', C(O)NR'2, NR'2, NO 2 , OR', SR', SO 2 , SOR', SO 3 R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, R 21 and R 2
  • R 31 -R 3 4 may each be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , CO 2 R', C(O)R', C(O)NR'2, NR'2, NO 2 , OR', SR', SO 2 , SOR', SO 3 R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, R 21 and R 22 , and two R 3 groups on adjacent ring atoms may form a fused 4-7- membered aromatic group, wherein said aromatic group may be cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said aromatic group may be optionally substituted by one or more substituents J; each substituent maybe R', CN, CF 3 , C(O)OR', C(O)R', C(O)NR' 2 , NR
  • L has the structure:
  • heteroleptic compounds which may be incorporated in
  • OLEDs having the structure:
  • L is a carbene ligand coordinated to iridium.
  • L has the structure:
  • L has the structure:
  • R 31 -R 34 may each be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , CO 2 R', C(O)R', C(O)NR'2, NR'2, NO 2 , OR', SR', SO 2 , SOR', SO 3 R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, R 21 and R 22j and two R 3 groups on adjacent ring atoms may form a fused 4-7- membered aromatic group, wherein said aromatic group may be cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said aromatic group may be optionally substituted by one or more substituents J
  • L has the structure:
  • the process includes the step of: (a) combining L with an organic solvent, wherein L is a suitable carbene ligand precursor; (b) maintaining the mixture of step (a) at a temperature from about 175°C to less than the boiling point of the organic solvent to obtain
  • step (c) recovering from the mixture. More preferably, the temperature at step (b) is at least about 185°C.
  • suitable carbene ligand precursor refers to a compound which may generate a free carbene, or a reactive equivalent thereof, under the conditions used to prepare the metal carbene complexes of the present invention. It is known to those skilled in the art that a variety of precursors may be used to generate carbene ligands, including imidazolium salts, silver complexes of carbene ligands, compounds wherein RO-H or Ar-H (where Ar is pentafluorophenyl or similar aryl) are eliminated from the same carbon to generate the carbene, and olefins formally corresponding to the product of carbene-carbene dimerization.
  • Tris(carbene)iridium complexes have previously been synthesized by reacting a carbene ligand with an organic solvent. These reactions, which are heated to a temperature well below 175°C, are not believed to produce chlorobridged dimers in quantities sufficient to be useful as starting materials for preparing homoleptic or heteroleptic iridium carbene complexes. It has been found that when the above process is heated to temperatures greater than about 175°C (but below the temperature at which the solvent boils), the reaction becomes unexpectedly selective for chlorobridged dimer complexes. These complexes have also been found to be useful for preparing heteroleptic carbene compounds having the formula L 2 lrL', as previously discussed.
  • the process comprise:
  • L has the structure:
  • A may be C or N;
  • X may be an alkyl group;
  • Y may be N, P, or C;
  • ring B may be an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring, wherein ring B may be optionally substituted with one or more substituents R 3 ;
  • ring B2 may be an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M, wherein ring B2 may be optionally substituted with one or more substituents Ra ;
  • Ri is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group;
  • R 21 , R 22 , R 3) Ra ls Ra 21 , Ra 2 2, Ra 23 , and Ra 3 are each independently selected from hydrogen, alkyl, alken
  • R 31 -R 4 and Ra 31 -Ra 34 may each be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF 3 , CO 2 R', C(O)R', C(O)NR'2, NR'2, NO 2 , OR', SR', SO 2 , SOR', SO 3 R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, R 21 and R 22; two R 3 groups, Ra !
  • each substituent J maybe independently selected from the group consisting of R', CN, CF 3 , C(O)OR', C(O)R', C(O)NR' 2 , NR' 2 , NO 2 , OR', SR', SO 2 , SOR', or SO 3 R', and additionally, or alternatively, two J groups on adjacent ring atoms may form a fused 4-7-membered aromatic group; each R' may be halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl.
  • L has the structure
  • Table 38 lists partial structures of carbene compounds ("A" part of the ligand), which in combination with the partial structures listed in Table 39 ("B" part of the ligand) make up additional embodiments.
  • representative embodiments include compounds having the core chemical structure of AxBy, wherein x is an integer from 1 to 47, preferably 1, 2, 5, 6, 7, 18, 19, 20, 33, or 35, and y is an integer from 1 to 86, preferably 1, 4, 10, 12, 55, 56, 59, 61, 62, 65, 66, 69, 70, 71, or 72.
  • the Rai substituent is an alkyl, an un-substituted aryl group, or an aryl group substituted with one or more electron donor groups, such as alkylamine, alkoxy, alkyl, or thiol groups, or electron acceptor groups, such as carboxylate, carbonyl, cyano, sulfoxide, sulfone, nitro, or phenyl groups, and the remaining Ra-substituents and Rb-substituents may be H, an alkyl group, an un-substituted aryl group, or an aryl group substituted with one or more electron donor or electron acceptor groups.
  • electron donor groups such as alkylamine, alkoxy, alkyl, or thiol groups
  • electron acceptor groups such as carboxylate, carbonyl, cyano, sulfoxide, sulfone, nitro, or phenyl groups
  • Preferred "B" parts of the carbene ligand include triphenylenes, e.g., B29 and
  • B46 fluorenes, e.g., B55-B60
  • carbazoles e.g., B61-B66
  • carbazole is a stable host and is used in hole transport layers in OLEDs.
  • Other "B" parts of the carbene ligand may be useful as red or green emitters or charge transporters.
  • heteroatom-carbon bonds are single bonds (e.g., B67, B70, B73, B76, and B79) rather than double bonds because it is believed that the heteroatom-carbon double bonds may be more susceptible to nucleophilic attacks which may lead to reduced device stability.
  • nitrogen containing heterocyclic rings with no formal double bonds to the nitrogen e.g., B67, B70, B73, B76, and B79 lead to better device stability.
  • Each specific individual compound may be represented as "AxBy-zl -z2," wherein zl-z2 is the compound number ("Cpd No.") as shown in the tables.
  • the prefix zl corresponds to the table number and the suffix z2 corresponds to the line number of that table, thus specifically identifying the individual compound.
  • Table 2 is used, since it lists specific embodiments for a structure having two available carbon atoms on the "A" part of the ligand and four available carbon atoms on the "B" part of the ligand.
  • Rai is methyl and Ra2, Ra3, Rbl, Rb2, Rb3 and Rb4 are each H; for "A1B1-2-2,” Rai and Rbl are each methyl and Ra2, Ra3, Rb2, Rb3 and Rb4 are each H; and for “A1B1-2-3,” Rai and Rb2 are each methyl and Ra2, Ra3, Rbl, Rb3 and Rb4 are each H.
  • m 3
  • there are known to be two stereo- isomers one that is typically referred to as the "mer” isomer and the other as the fac" isomer.
  • the mixture of both isomers is identified as "AxBy-zl-z2,” whereas the "mer” isomer is identified as “mer- AxBy-zl-z2,” and the "fac” isomer, as ' ⁇ c-AxBy-zl-z2.”
  • steric considerations may either limit or favor the synthesis of particular embodiments. For example, having large bulky groups on adjacent positions could hinder the synthesis of certain compounds. Alternatively, there may be particular groups that improve ease of synthesis, solubility, sublimation temperature, and/or thermal stability of certain compounds.
  • the methyl groups that are on the methylene carbon of fluorene groups for example, the R7 and R8 positions on B55, or on the N-atom of the carbazole group, for example, the R7 position of B61, the methyl groups that are shown in the tables at these positions may instead readily be phenyl groups that form highly stable compounds.
  • the phosphorescent material may be a compound having the core chemical structure of A2B1, wherein M is Ir, m
  • the phosphorescent material may be a compound having the core chemical structure of A2B4, wherein M is Ir, m
  • the phosphorescent material may be a compound having the core chemical structure of A5B1, wherein M is Ir, m
  • the phosphorescent material may be a compound having the core chemical structure of A5B4, wherein M is Ir, m
  • the phosphorescent material may be a compound having the core chemical structure of A6B1, wherein M is Ir, m
  • the phosphorescent material may be a compound having the core chemical structure of A6B4, wherein M is Ir, m
  • the phosphorescent material may be a compound having the core chemical structure of A7B1, wherein M is Ir, m
  • the phosphorescent material may be a compound having the core chemical structure of A7B4, wherein M is Ir, m
  • A35B12 being listed in Table 20.
  • A35B70 being listed in Table 24.
  • any one of the preceding specific representative embodiments may be selected so as to achieve particular desired device characteristics, for example, emission color, stability, HOMO and/or LUMO energy levels, and/or electron or hole trapping properties of the material.
  • any one of the preceding specific representative embodiments may be further substituted, for example, with additional electron donor or electron acceptor groups, so as to further adjust certain device properties, such as emission color or stability.
  • any one of the compounds referred to in Tables 1-37 may include one or more additional methyl or phenyl groups, and/or the methyl and/or phenyl groups may be replaced with other aryl or alkyl groups such as ethyl or t-butyl.
  • one or more of the AxBy ligands of the tr/s-iridium compound may be replaced with an ancillary "X-Y" ligand, also so as to further adjust the specific device properties, such as emission color or stability.
  • the ancillary "X-Y" ligand may be one or more ligands selected from the group consisting of mono-dentate, bi-dentate, tri-dentate or tetra-dentate ligands.
  • the ancillary ligand may be another organometallic ligand, such as another carbene ligand, or a non-organometallic ligand, such as acetoacetonate and others previously mentioned.
  • the iridium atom of any one of the preceding specific representative embodiments may be replaced with another metal atom so as to further adjust particular device properties, such as emission color or stability.
  • the metal atom, other than Ir may be any 3 rd row transition metals, preferably Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, or Ag, more preferably, Pt, Rh, Re, Au, Os, or Ru, and most preferably, Pt.
  • any one of the specific representative embodiments may be selected, as listed, or as further modified, so that the materials may be used as an ETL, an HTL, a hole blocking layer, an electron blocking layer, or an exciton blocking layer.
  • the compounds may be selected, and/or modified, so as to improve the electron and/or hole conductivity of the material.
  • the carbene-carbon atom that is bound to the metal atom may in some cases be conjugated with a quatemized N-alkyl unit, which in combination with the carbene-carbon atom may be drawn as a valid zwitter-ion resonance structure, with the carbene-carbon atom and the quatemized nitrogen atom being part of a heterocyclic aromatic ring, such as described in Take-aki Koizumi et al., "Terpyridine- Analogous (N,N,C)-Tridentate Ligands; Synthesis, Structures, and Electrochemical Properties of Ruthenium (II) Complexes Bearing Tridentate Pyridinium and Pyridinylidene Ligands," Organometallics, Vol 22, pp.
  • a carbene may be properly characterized as having a valid zwitter-ion resonance structure
  • such a ligand is represented, for example, by the ligands that include the B19 unit as part of the ligand.
  • One of the unifying features of the preferred representative embodiments that are specifically disclosed herein is that they all have as a core part of their chemical structure a cyclometallated, five-member, ring, which includes a metal atom bound to two carbon atoms within the ring, wherein one of the metal-carbon bonds is a metal-carbene bond and the other is a metal-mono-anionic carbon bond.
  • Such structures are analogous to the metal-ppy- based complexes that are typically used in phosphorescent OLEDs.
  • Such metal-ppy-based chemical structures also have a cyclometallated, five-member, ring as a core part of their chemical structure, except that the metal is bound to a single carbon atom, via a metal-mono- anionic carbon bond, and to a nitrogen atom instead of a carbene carbon. Because of the close structural analogy between the carbene-based complexes disclosed herein and metal- ppy-based complexes, it is believed herein that selection of the specifically preferred AxBy complexes may be based on considerations similar to those used to selected the preferred metal-ppy-based complexes.
  • iridium and platinum are the most commonly preferred metals of the phosphorescent metal-ppy-based complexes, due to the very high spin-orbit coupling between the metal atom and the carbon atom, these same two metals are the most preferred metals for use in combination with the carbene-based ligands, but with iridium being more highly preferred.
  • metal-carbene bond with its unique chemical characteristics, will lead to further particular benefits and advantages that are unique to metal-carbene complexes, and that may not be readily predicted based on their metal-ppy-based analogues.

Abstract

An organic light emitting device is provided. The device has an anode, a cathode and an organic layer disposed between the anode and the cathode. The organic layer comprises a compound further comprising one or more carbene ligands coordinated to a metal center.

Description

LUMINESCENT COMPOUNDS WITH CARBENE LIGANDS
[0001] This application is related to U.S. Application No. 10/880,384, filed June 28,
2004, entitled Luminescent Compounds with Carbene Ligands, which is a continuation-in- part of U.S. Application No. 10/849,301, filed May 18, 2004; to U.S. Application No.
11/032,885, filed January 10, 2005, entitled Novel Organometallic Compounds for Use in Electroluminescent Devices; U.S. Application No. 11/032,887, filed January 10, 2005, entitled Carbene Metal Complexes as OLED Materials; U.S. Application No. 11/032,836, filed January 10, 2005, entitled Cyclometallated Iridium Carbene Complexes for Use as Hosts; U.S. Application No. 11/032,950, filed January 10, 2005, entitled Complexes with Tridentate Ligands; U.S. Application No. 11/032,721, filed January 10, 2005, entitled Cationic Metal-Carbene Complexes; U.S. Application No. 11/031,078, filed January 10,
2005, entitled OLEDs Utilizing Macrocyclic Ligand Systems; U.S. Application No. 11/030,901, filed January 10, 2005, entitled OLEDs Utilizing Macrocyclic Ligand Systems; U.S. Application No. 11/032,739, filed January 10, 2005, entitled Carbene Containing Metal Complexes as OLEDs; and U.S. Application No. 11/032,941, filed January 10, 2005, entitled Reversibly Reducible Metal Complexes as Electron Transporting Materials for OLEDs.
Research Agreements
[0002] The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Princeton University, The University of Southern California and Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.
Field of the Invention
[0003] The present invention relates to organic light emitting devices (OLEDs), and more specifically to phosphorescent organic materials used in such devices. More specifically, the present invention relates to carbene-metal complexes incorporated into OLEDs.
Background
[0004] Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants. [0005] As used herein, the term "organic" includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecules" may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the "small molecule" class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a "small molecule," and it is believed that all dendrimers currently used in the field of OLEDs are small molecules. In general, a small molecule has a well-defined chemical formula with a single molecular weight, whereas a polymer has a chemical formula and a molecular weight that may vary from molecule to molecule. As used herein, "organic" includes metal complexes of hydrocarbyl and heteroatom-substituted hydrocarbyl ligands. [0006] OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Patent Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entireties. [0007] OLED devices are generally (but not always) intended to emit light through at least one of the electrodes, and one or more transparent electrodes may be useful in organic opto-electronic devices. For example, a transparent electrode material, such as indium tin oxide (ITO), may be used as the bottom electrode. A transparent top electrode, such as disclosed in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, may also be used. For a device intended to emit light only through the bottom electrode, the top electrode does not need to be transparent, and may be comprised of a thick and reflective metal layer having a high electrical conductivity. Similarly, for a device intended to emit light only through the top electrode, the bottom electrode may be opaque and / or reflective. Where an electrode does not need to be transparent, using a thicker layer may provide better conductivity, and using a reflective electrode may increase the amount of light emitted through the other electrode, by reflecting light back towards the transparent electrode. Fully transparent devices may also be fabricated, where both electrodes are transparent. Side emitting OLEDs may also be fabricated, and one or both electrodes may be opaque or reflective in such devices.
[0008] As used herein, "top" means furthest away from the substrate, while "bottom" means closest to the substrate. For example, for a device having two electrodes, the bottom electrode is the electrode closest to the substrate, and is generally the first electrode fabricated. The bottom electrode has two surfaces, a bottom surface closest to the substrate, and a top surface further away from the substrate. Where a first layer is described as "disposed over" a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is "in physical contact with" the second layer. For example, a cathode may be described as "disposed over" an anode, even though there are various organic layers in between.
[0009] As used herein, "solution processible" means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
[0010] As used herein, and as would be generally understood by one skilled in the art, a first "Highest Occupied Molecular Orbital" (HOMO) or "Lowest Unoccupied Molecular Orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A "higher" HOMO or LUMO energy level appears closer to the top of such a diagram than a "lower" HOMO or LUMO energy level. [0011] The carbene ligand has been well known in organometallic chemistry, and is used to generate a wide range of thermally stable catalytic materials. The carbene ligands have been employed both as active groups, directly engaged in the catalytic reactions, and serving a role of stabilizing the metal in a particular oxidation state or coordination geometry. However, applications of carbene ligands are not well known in photochemistry. [0012] One issue with many existing organic electroluminescent compounds is that they are not sufficiently stable for use in commercial devices. An object of the invention is to provide a class of organic emissive compounds having improved stability. [0013] In addition, existing compounds do not include compounds that are stable emitters for high energy spectra, such as a blue spectra. An object of the invention is to provide a class of organic emissive compounds that can emit light with various spectra, including high energy spectra such as blue, in a stable manner.
Summary of the Invention
[0014] An organic light emitting device is provided. The device has an anode, a cathode and an organic layer disposed between the anode and the cathode. The organic layer comprises a compound further comprising one or more carbene ligands coordinated to a metal center.
[0015] In one aspect, the organic layer comprises a compound having at least one zwitterionic carbon donor ligand.
[0016] In another aspect, he organic layer comprises a host and a dopant, and the host comprises a compound having at least one carbene atom coordinated to iridium, and the compound has the structure:
Figure imgf000006_0001
[0017] In another aspect, the organic layer comprises a reversibly reducible metal complex of a redox active metal center and at least one ligand, where, in a reduced state, an extra electron is localized on the metal center. The redox active metal complex, i.e., the reversibly reducible metal complex, may function as an ETL and/or as a host for an emissive material. Preferred reducible metal complexes in accordance with the invention are of Formula I
and Formula II
Figure imgf000006_0002
[0018] Redox active metal complexes in accordance with the invention include, but are not limited to, reversibly reducible metal complexes of formula:
Figure imgf000006_0003
Figure imgf000007_0001
Figure imgf000008_0001
ι
Figure imgf000008_0003
Figure imgf000008_0002
[0019] In another aspect, the organic layer comprises a carbene ligand bound to a metal center, wherein the resulting metal-carbene complex is cationic. [0020] In another aspect, the organic layer comprises at least one tridentate ligand bound to a metal center through at least one carbene-metal bond. Preferably, the organic layer comprises two tridentate ligands, which may be the same or different, bound to the metal center, wherein at least one of the tridentate ligands has a carbene-metal bond. More preferably, the organic layer comprises an emissive material having the formulae:
Figure imgf000009_0001
[0001] In another aspect, the organic layer comprises an organometallic compound further comprising a macrocyclic ligand coordinated to a metal center. In one embodiment, the macrocyclic ligand is planar. In another embodiment, the macrocyclic ligand is a tetradentate ligand. In another embodiment, the macrocyclic tetradentate ligand comprises two 5-membered rings and two 6-membered rings, each coordinated to the metal center. [0002] In another aspect, the organic layer comprises a macrocyclic compound having the structures:
Figure imgf000010_0001
[0022] In one aspect, a process for preparing a compound having the formula L2IrL' is provided. The process comprises:
(a) combining
Figure imgf000011_0001
in the presence of an organic solvent to form a mixture, wherein L is a carbene ligand coordinated to Ir; and L' is a bidentate ligand or two monodentate ligands, and L is different from L'; (b) maintaining the mixture for sufficient time to obtain L IrL' ;
(c) recovering L2IrL' from the mixture.
[0023] In another aspect, a process for preparing a compound having the formula
Figure imgf000011_0002
, is provided. The process comprises:
(a) combining L with an organic solvent, wherein L is a suitable carbene ligand precursor; (b) maintaining the mixture of step (a) at a temperature from about 175°C to less
than the boiling point ofthe organic solvent in (a) to obtain
Figure imgf000011_0003
; and
(c) recovering
Figure imgf000011_0004
from the mixture.
[0024] A process for preparing a compound with the formula L3Ir is also provided in another aspect. This process comprises:
(a) combining
Figure imgf000011_0005
and L in the presence of alcohol and a base to form a mixture, wherein L is a bidentate ligand that may form a five-membered chelate ring; (b) maintaining the mixture for sufficient time to obtain L3Ir; and
(c) recovering L3Ir from the mixture. [0025] Compounds prepared from the above processes may be incorporated into
OLEDs.
Brief Description of the Drawings
[0026] Fig. 1 shows an organic light emitting device having separate electron transport, hole transport, and emissive layers, as well as other layers.
[0027] Fig. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.
[0028] Fig. 3 shows the 1H NMR spectra of mer-(F2ppz)2Ir(l -Ph-3 -Me-imid) in
CDC13.
[0029] Fig. 4 shows the 1H NMR spectra of mer-(tpy)2Ir(l -Ph-3 -Me-imid) in CDC13.
[0030] Fig. 5 shows the 1H NMR spectra of fac-(tpy)2Ir(l -Ph-3 -Me-imid) in CDC13.
[0031] Fig. 6 shows the plot of current (μA) vs. voltage (V) of amer-(tpy)2Ir(l-Ph-3-
Me-imid) device with ferrocene as an internal reference. A solvent of DMF with O.IM
Bu N+PF6 " is used.
[0032] Fig. 7 shows the plot of current (μA) vs. voltage (V) of a fac-(tpy)2Ir(l -Ph-3-
Me-imid) device with ferrocene as an internal reference. A solvent of DMF with 0.1M
Bu4N PF6" is used.
[0033] Fig. 8 shows the absorption spectra of fac-(tpy)2Ir(l -Ph-3 -Me-imid) and mer-
(tpy)2Ir(l-Ph-3-Me-imid) in CH2C12.
[0034] Fig. 9 shows the emission spectra of mer-(tpy)2Ir(l -Ph-3 -Me-imid) in 2-
MeTHF at room temperature and at 77K. The compound exhibits lifetimes of 1.7 μs at room temperature and 3.3 μs at 77K.
[0035] Fig. 10 shows the emission spectra of fac-(tpy)2Ir(l -Ph-3 -Me-imid) in 2-
MeTHF at room temperature and at 77K. The compound exhibits lifetimes of 1.7 μs at room temperature and 3.3 μs at 77K.
[0036] Fig. 11 shows the 1H NMR spectra of [(l-Ph-3-Me-imid)2IrCl]2 in CDC13.
[0037] Fig. 12 shows the 1H NMR spectra of (l-Ph-3-Me-imid)2Ir(t-Bu-bpy)+ in
CDC13.
[0038] Fig. 13 shows the absorption spectra of (l-Ph-3-Me-imid)2Ir(t-Bu-bpy)+ in
CH2C12. [0039] Fig. 14 shows the emission spectra of (l-Ph-3-Me-imid)2Ir(t-Bu-bpy)+ in 2-
MeTHF at 77K and (l-Ph-3-Me-imid)2rr(t-Bu-bρy)+ in CH2C12 at room temperature. The compound exhibits lifetimes of 0.70 μs at room temperature and 6.0 μs at 77K.
[0040] Fig. 15 shows the 1H NMR spectra of mer-Ir(l-Ph-3-Me-imid)3 in CDC13.
[0041] Fig. 16 shows the 13C NMR spectra of mer-Ir(l-Ph-3-Me-imid)3 in CDC13.
[0042] Fig. 17 shows the plot of current (μA) vs. voltage (V) of a mer-Ir(l-Ph-3-Me- imid) device with ferrocene as an internal reference. A solvent of DMF with 0.1M
Figure imgf000013_0001
is used.
[0043] Fig. 18 shows the emission spectra of mer-Ir(l-Ph-3-Me-imid)3 in 2-MeTHF at room temperature and at 77K.
[0044] Fig. 19 shows the 1H NMR spectra of fac-Ir(l-Ph-3-Me-imid)3 in CDC13.
[0045] Fig. 20 shows the absorption spectra of fac-Ir(l-Ph-3-Me-imid)3 in CH C1 .
[0046] Fig. 21 shows the emission spectra of fac-rr(l-Ph-3-Me-imid)3 in 2-MeTHF at room temperature and at 77K. The device exhibits lifetimes of 0.50 μs at room temperature and 6.8 μs at 77K.
[0047] Fig. 22 shows the 1H NMR spectra of 1 -Ph-3 -Me-benzimid in CDC13.
[0048] Fig. 23 shows the 1H NMR spectra of fac-Ir(l -Ph-3 -Me-benzimid)3 in CDC13.
[0049] Fig. 24 shows the plot of current (mA) vs. voltage (V) of a fac-Ir(l-Ph-3-Me- benzimid) device with ferrocene as an internal reference. A solvent of anhydrous DMF is used.
[0050] Fig. 25 shows the emission spectra of fac-Ir(l-Ph-3-Me-benzimid)3 in 2-
MeTHF at room temperature and at 77K. The device emits a spectrum at CIE 0.17, 0.04.
[0051] Fig. 26 shows the emission spectra of (Ir-Fl-Me-imid)3 in 2-MeTHF at room temperature and at 77K. The device exhibits lifetimes of 5 μs at room temperature and 35 μs at 77K.
[0052] Figure 27 shows the external quantum efficiency vs. current density of examples 20-21 and comparative example 1.
[0053] Figure 28 shows the electroluminescence spectra of examples 20-21 and comparative example 1 at 10 mA/cm .
[0054] Figure 29 shows the operational stability of example 20 vs comparative example 1.
[0055] Figure 30 shows the external quantum efficiency vs. current density of examples 22-25. [0056] Figure 31 shows the electroluminescence spectra of examples 22-25.
[0057] Figure 32 shows the external quantum efficiency vs. current density of examples 26-29.
[0058] Figure 33 shows the electroluminescence spectra of examples 26-29.
[0059] Figure 34 shows the external quantum efficiency vs. current density of examples 30 and 31.
[0060] Figure 35 shows the electroluminescence spectra of examples 30 and 31.
[0061] Figure 36 shows the external quantum efficiency vs. current density of example 32.
[0062] Figure 37 shows the electroluminescence spectra of example 32.
[0063] Figure 38 shows the external quantum efficiency vs. current density of example 33.
[0064] Figure 39 shows the electroluminescence spectra of example 33.
[0065] Figure 40 shows the external quantum efficiency vs. current density of example 34 and 35.
[0066] Figure 41 shows the electroluminescence spectra of example 34 and 35.
[0067] Figure 42 shows the subtracted EL spectra of example 34 from example 35.
[0068] Figure 43 shows the quantum efficiency vs. current density for comparative example 4.
[0069] Figure 44 shows the normalized electroluminescent spectra for comparative example 4.
[0070] Fig. 45 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/UGH5: Dopant A (6%, 300)/BAlQ(400) and device
CuPc(100)/NPD(300)/UGH5: Dopant B (6%, 300)/BAlQ(400).
[0071] Fig. 46 shows plots of quantum efficiency vs. current density for device
CuPc(100)/NPD(300)/UGH5: Dopant A (6%, 300)/BAlQ(400) and device
CuPc(100)/NPD(300)/UGH5: Dopant B (6%, 300)/BAlQ(400).
[0072] Fig. 47 shows plots of the electroluminescent spectra of device
CuPc(100)/NPD(300)/UGH5: Dopant A (6%, 300)/BAlQ(400) and device
CuPc(100)/NPD(300)/UGH5: Dopant B (6%, 300)/BAlQ(400).
[0073] Fig. 48 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/mCBP: Dopant C (6%, 300)/BAlQ(400) and device
CuPc(100)/NPD(300)/mCBP:Dopant D (6%, 300)/BA1Q(400). [0074] Fig. 49 shows plots of quantum efficiency vs. current density for device
CuPc(100)/NPD(300)/mCBP: Dopant C (6%, 300)/BAlQ(400) and device
CuPc(100)/NPD(300)/mCBP: Dopant D (6%, 300)/BAlQ(400).
[0075] Fig. 50 shows plots of the electroluminescent spectra of device
CuPc(100)/NPD(300)/mCBP: Dopant C (6%, 300)/BAlQ(400) and device
CuPc(100)/NPD(300)/mCBP: Dopant D (6%, 300)/BAlQ(400).
[0076] Fig. 51 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/mCBP: Dopant E (300, 6%)/BAlQ(400) and device
CuPc(100)/NPD(300)/mCBP: Dopant F (300, 6%)/BAlQ(400).
[0077] Fig. 52 shows plots of quantum efficiency vs. current density for device
CuPc(100)/NPD(300)/mCBP: Dopant E (300, 6%)/BAlQ(400) and device
CuPc(100)/NPD(300)/mCBP: Dopant F (300, 6%)/BAlQ(400).
[0078] Fig. 53 shows plots of the electroluminescent spectra of device
CuPc(100)/NPD(300)/mCBP: Dopant E (300, 6%)/BAlQ(400) and device
CuPc(100)/NPD(300)/mCBP: Dopant F (300, 6%)/BAlQ(400).
[0079] Fig. 54 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/UGH5: Dopant G (6%, 300)/BAlQ(400).
[0080] Fig. 55 shows plots of quantum efficiency vs. current density for
CuPc(100)/NPD(300)/UGH5: Dopant G (6%, 300)/BAlQ(400).
[0081] Fig. 56 shows plots of the electroluminescent spectra of
CuPc(100)/NPD(300)/UGH5: Dopant G (6%, 300)/BAlQ(400).
[0082] Fig. 57 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/mCP: Dopant H (6%, 300)/BAlQ(400), device
CuPc(100)/NPD(300)/CBP: Dopant 1(6%, 300)/BAlQ(400), and device
CuPc(100)/NPD(300)/mCBP: Dopant J (6%, 300)/BAlQ(400).
[0083] Fig. 58 shows plots of quantum efficiency vs. current density for device
CuPc(100)/NPD(300)/mCP: Dopant H (6%, 300)/BAlQ(400), device
CuPc(100)/NPD(300)/CBP: Dopant I (6%, 300)/BAlQ(400), and device
CuPc(100)/NPD(300)/mCBP: Dopant J (6%, 300)/BAlQ(400).
[0084] Fig. 59 shows plots of the electroluminescent spectra of device
CuPc(100)/NPD(300)/mCP: Dopant H (6%, 300)/BAlQ(400), device
CuPc(100)/NPD(300)/CBP: Dopant I (6%, 300)/BAlQ(400), and device
CuPc(100)/NPD(300)/mCBP: Dopant J (6%, 300)/BAlQ(400). [0085] Fig. 60 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/mCBP: Dopant K (6%, 300)/BAlQ(400), device
CuPc(100)/NPD(300)/mCBP: Dopant L (6%, 300)/BAlQ(400), and device
CuPc(100)/NPD(300)/UGH5: Dopant M (6%, 300)/BAlQ(400).
[0086] Fig. 61 shows plots of quantum efficiency vs. current density for device
CuPc(100)/NPD(300)/mCBP: Dopant K (6%, 300)/BAlQ(400), device
CuPc(100)/NPD(300)/mCBP: Dopant L (6%, 300)/BAlQ(400), and device
CuPc(100)/NPD(300)/UGH5: Dopant M (6%, 300)/BAlQ(400).
[0087] Fig. 62 shows plots of the electroluminescent spectra of device
CuPc(100)/NPD(300)/mCBP: Dopant K (6%, 300)/BA1Q(400), device
CuPc(100)/NPD(300)/mCBP: Dopant L (6%, 300)/BAlQ(400), and device
CuPc(100)/NPD(300)/UGH5: Dopant M (6%, 300)/BAlQ(400).
[0088] Fig. 63 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/UGH5: Dopant N (6%, 300)/BAlQ(400), device
CuPc(100)/NPD(300)/UGH5: Dopant O (6%, 300)/BAlQ(400), and device
CuPc(100)/NPD(300)/UGH5: Dopant P (6%, 300)/BAlQ(400).
[0089] Fig. 64 shows plots of quantum efficiency vs. current density for device
CuPc(100)/NPD(300)/UGH5: Dopant N (6%, 300)/BAlQ(400), device
CuPc(100)/NPD(300)/UGH5: Dopant O (6%, 300)/BAlQ(400), and device
CuPc(100)/NPD(300)/UGH5: Dopant P (6%, 300)/BAlQ(400).
[0090] Fig. 65 shows plots of the electroluminescent spectra of device
CuPc(100)/NPD(300)/UGH5: Dopant N (6%, 300)/BAlQ(400), device
CuPc(100)/NPD(300)/UGH5: Dopant O (6%, 300)/BAlQ(400), and device
CuPc(100)/NPD(300)/UGH5: Dopant P (6%, 300)/BAlQ(400).
[0091] Fig. 66 shows plots of the plot of operation lifetime of device
CuPc(100)/NPD(300)/UGH5: Dopant D (6%, 300)/BAlQ(400).
[0092] Fig. 67 shows plots of current vs. voltage of device CuPc(l 00 A)/NPD(300
A)/mCP:Dopant Q(300 A,6%)/BA1Q(400 A) and device CuPc(100 A)/NPD(300 A)/mCP:
Dopant Q (300 A,6%)/HPT(100 A)/BA1Q(400 A).
[0093] Fig. 68 shows plots of quantum efficiency vs. current density for device
CuPc(100 A)/NPD(300 A)/mCP: Dopant Q (300 A,6%)/BA1Q(400 A) and device CuPc(100
A)/NPD(300 A)/mCP: Dopant Q (300 A,6%)/HPT(100 A)/BA1Q(400 A). [0094] Fig. 69 shows the electroluminescent spectra for device CuPc(100
A)/NPD(300 A)/mCP: Dopant Q (300 A,6%)/BA1Q(400 A) and device CuPc(100
A)/NPD(300 A)/mCP: Dopant Q (300 A,6%)/HPT(100 A)/BA1Q(400 A).
[0095] Fig. 70 shows plots of current vs. voltage of device CuPc(100 A)/NPD(300
A)/ UGH5: Dopant Q (300 A,12%)/BA1Q(400 A) and device CuPc(100 A)/NPD(300 A)/
TCTA(100 A)/UGH5: Dopant Q (300 A,12%)/BA1Q(400 A).
[0096] Fig. 71 shows plots of quantum efficiency vs. current density for device
CuPc(100 A)/NPD(300 A)/ UGH5: Dopant Q (300 A,12%)/BA1Q(400 A) and device
CuPc(100 A)/NPD(300 A)/ TCTA(100 A)/UGH5: Dopant Q (300 A,12%)/BA1Q(400 A).
[0097] Fig. 72 shows the electroluminescent spectra for device CuPc(100
A)/NPD(300 A)/ UGH5: Dopant Q (300 A,12%)/BA1Q(400 A) and device CuPc(100
A)/NPD(300 A)/ TCTA(100 A)/UGH5: Dopant Q (300 A,12%)/BA1Q(400 A).
[0098] Fig. 73 shows plots of operational lifetime of device CuPc(100 A)/NPD(300
A)/mCP: Dopant Q (300 A,6%)/BA1Q(400 A) and device CuPc(100 A)/NPD(300 A)/mCP:
Dopant Q (300 A,6%)/HPT(100 A)/BA1Q(400 A) measured at 5 mA cm2.
[0099] Figure 74 shows plots of the current density vs. voltage for device Examples
56 and 57.
[0100] Fig. 75 shows plots of the quantum efficiency vs. current density for device
Examples 56 and 57.
[0101] Fig. 76 shows plots of the electroluminescent spectra for device Examples 56 and 57.
[0102] Fig. 77 shows plots of current density vs. voltage for device Examples 58 and
59.
[0103] Fig. 78 shows plots of the quantum efficiency vs. current density for device
Examples 58 and 59.
[0104] Fig. 79 shows plots of the electroluminescent spectra for device Examples 58 and 59.
[0105] Fig. 80 shows plots of operation lifetime of device Examples 56, 58, and 59.
[0106] Fig. 81 shows the emission spectra for compound Osl.
[0107] Fig. 82 shows the emission spectra for compound Os2.
[0108] Fig. 83 shows the room temperature emission spectrum for compound Pt 151.
Detailed Description [0109] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an "exciton," which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
[0110] The initial OLEDs used emissive molecules that emitted light from their singlet states ("fluorescence") as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
[0111] More recently, OLEDs having emissive materials that emit light from triplet states ("phosphorescence") have been demonstrated. Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Nature, vol. 395, 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence," Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) ("Baldo-II"), which are incorporated by reference in their entireties. Phosphorescence may be referred to as a "forbidden" transition because the transition requires a change in spin states, and quantum mechanics indicates that such a transition is not favored. As a result, phosphorescence generally occurs in a time frame exceeding at least 10 nanoseconds, and typically greater than 100 nanoseconds. If the natural radiative lifetime of phosphorescence is too long, triplets may decay by a non-radiative mechanism, such that no light is emitted. Organic phosphorescence is also often observed in molecules containing heteroatoms with unshared pairs of electrons at very low temperatures. 2,2'-bipyridine is such a molecule. Non-radiative decay mechanisms are typically temperature dependent, such that an organic material that exhibits phosphorescence at liquid nitrogen temperatures typically does not exhibit phosphorescence at room temperature. But, as demonstrated by Baldo, this problem may be addressed by selecting phosphorescent compounds that do phosphoresce at room temperature. Representative emissive layers include doped or un- doped phosphorescent organometallic materials such as disclosed in U.S. Patent Nos. 6,303,238; 6,310,360; 6,830,828; and 6,835,469; U.S. Patent Application Publication Nos. [0112] Generally, the excitons in an OLED are believed to be created in a ratio of about 3:1, i.e., approximately 75% triplets and 25% singlets. See, Adachi et al., "Nearly 100% Internal Phosphorescent Efficiency In An Organic Light Emitting Device," J. Appl. Phys., 90, 5048 (2001), which is incorporated by reference in its entirety. In many cases, singlet excitons may readily transfer their energy to triplet excited states via "intersystem crossing," whereas triplet excitons may not readily transfer their energy to singlet excited states. As a result, 100% internal quantum efficiency is theoretically possible with phosphorescent OLEDs. In a fluorescent device, the energy of triplet excitons is generally lost to radiationless decay processes that heat-up the device, resulting in much lower internal quantum efficiencies. OLEDs utilizing phosphorescent materials that emit from triplet excited states are disclosed, for example, in U.S. Patent No. 6,303,238, which is incorporated by reference in its entirety.
[0113] Phosphorescence may be preceded by a transition from a triplet excited state to an intermediate non-triplet state from which the emissive decay occurs. For example, organic molecules coordinated to lanthanide elements often phosphoresce from excited states localized on the lanthanide metal. However, such materials do not phosphoresce directly from a triplet excited state but instead emit from an atomic excited state centered on the lanthanide metal ion. The europium diketonate complexes illustrate one group of these types of species.
[0114] Phosphorescence from triplets can be enhanced over fluorescence by confining, preferably through bonding, the organic molecule in close proximity to an atom of high atomic number. This phenomenon, called the heavy atom effect, is created by a mechanism known as spin-orbit coupling. Such a phosphorescent transition may be observed from an excited metal-to-ligand charge transfer (MLCT) state of an organometallic molecule such as tris(2-phenylpyridine)iridium(III).
[0115] As used herein, the term "triplet energy" refers to an energy corresponding to the highest energy feature discernable in the phosphorescence spectrum of a given material. The highest energy feature is not necessarily the peak having the greatest intensity in the phosphorescence spectrum, and could, for example, be a local maximum of a clear shoulder on the high energy side of such a peak.
[0116] The term "organometallic" as used herein is as generally understood by one of ordinary skill in the art and as given, for example, in "Inorganic Chemistry" (2nd Edition) by Gary L. Miessler and Donald A. Tarr,- Prentice Hall (1998). Thus, the term organometallic refers to compounds which have an organic group bonded to a metal through a carbon-metal bond. This class does not include per se coordination compounds, which are substances having only donor bonds from heteroatoms, such as metal complexes of amines, halides, pseudohalides (CN, etc.), and the like. In practice organometallic compounds generally comprise, in addition to one or more carbon-metal bonds to an organic species, one or more donor bonds from a heteroatom. The carbon-metal bond to an organic species refers to a direct bond between a metal and a carbon atom of an organic group, such as phenyl, alkyl, alkenyl, etc., but does not refer to a metal bond to an "inorganic carbon," such as the carbon ofCN or CO.
[0117] Figure 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, and a cathode 160. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order.
[0118] Substrate 110 may be any suitable substrate that provides desired structural properties. Subsfrate 110 may be flexible or rigid. Substrate 110 may be transparent, translucent or opaque. Plastic and glass are examples of preferred rigid substrate materials. Plastic and metal foils are examples of preferred flexible substrate materials. Substrate 110 may be a semiconductor material in order to facilitate the fabrication of circuitry. For example, substrate 110 may be a silicon wafer upon which circuits are fabricated, capable of controlling OLEDs subsequently deposited on the substrate. Other substrates may be used. The material and thickness of substrate 110 may be chosen to obtain desired structural and optical properties.
[0119] Anode 115 may be any suitable anode that is sufficiently conductive to transport holes to the organic layers. The material of anode 115 preferably has a work function higher than about 4 eV (a "high work function material"). Preferred anode materials include conductive metal oxides, such as indium tin oxide (ITO) and indium zinc oxide (IZO), aluminum zinc oxide (AlZnO), and metals. Anode 115 (and substrate 110) may be sufficiently transparent to create a bottom-emitting device. A preferred transparent substrate and anode combination is commercially available ITO (anode) deposited on glass or plastic (substrate). A flexible and transparent substrate-anode combination is disclosed in United States Patent Nos. 5,844,363 and 6,602,540 B2, which are incorporated by reference in their entireties. Anode 115 may be opaque and / or reflective. A reflective anode 115 may be preferred for some top-emitting devices, to increase the amount of light emitted from the top of the device. The material and thickness of anode 115 may be chosen to obtain desired conductive and optical properties. Where anode 115 is transparent, there may be a range of thickness for a particular material that is thick enough to provide the desired conductivity, yet thin enough to provide the desired degree of transparency. Other anode materials and structures may be used.
[0120] Hole transport layer 125 may include a material capable of transporting holes.
Hole transport layer 130 may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. α-NPD and TPD are examples of intrinsic hole transport layers. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in United States Patent Application Publication No. 2003-0230980 to Forrest et al., which is incorporated by reference in its entirety. Other hole transport layers may be used.
[0121] Emissive layer 135 may include an organic material capable of emitting light when a current is passed between anode 115 and cathode 160. Preferably, emissive layer 135 contains a phosphorescent emissive material, although fluorescent emissive materials may also be used. Phosphorescent materials are preferred because of the higher luminescent efficiencies associated with such materials. Emissive layer 135 may also comprise a host material capable of transporting electrons and / or holes, doped with an emissive material that may trap electrons, holes, and / or excitons, such that excitons relax from the emissive material via a photoemissive mechanism. Emissive layer 135 may comprise a single material that combines transport and emissive properties. Whether the emissive material is a dopant or a major constituent, emissive layer 135 may comprise other materials, such as dopants that tune the emission of the emissive material. Emissive layer 135 may include a plurality of emissive materials capable of, in combination, emitting a desired spectrum of light. Examples of phosphorescent emissive materials include Ir(ρpy)3. Examples of fluorescent emissive materials include DCM and DMQA. Examples of host materials include Alq3, CBP and mCP. Examples of emissive and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. Emissive material may be included in emissive layer 135 in a number of ways. For example, an emissive small molecule may be incorporated into a polymer. This may be accomplished by several ways: by doping the small molecule into the polymer either as a separate and distinct molecular species; or by incorporating the small molecule into the backbone of the polymer, so as to form a co-polymer; or by bonding the small molecule as a pendant group on the polymer. Other emissive layer materials and structures may be used. For example, a small molecule emissive material may be present as the core of a dendrimer. [0122] Many useful emissive materials include one or more ligands bound to a metal center. A ligand may be referred to as "photoactive" if it contributes directly to the luminescent properties of an organometallic emissive material. A "photoactive" ligand may provide, in conjunction with a metal, the energy levels from which and to which an electron moves when a photon is emitted. Other ligands may be referred to as "ancillary." Ancillary ligands may modify the photoactive properties of the molecule, for example by shifting the energy levels of a photoactive ligand, but ancillary ligands do not directly provide the energy levels involved in light emission. A ligand that is photoactive in one molecule may be ancillary in another. These definitions of photoactive and ancillary are intended as non- limiting theories.
[0123] Electron transport layer 145 may include a material capable of transporting electrons. Electron transport layer 145 may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Alq3 is an example of an intrinsic electron transport layer. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1 :1, as disclosed in United States Patent Application Publication No. 2003-0230980 to Forrest et al., which is incorporated by reference in its entirety. Other electron transport layers may be used.
[0124] The charge carrying component of the electron transport layer may be selected such that electrons can be efficiently injected from the cathode into the LUMO (Lowest Unoccupied Molecular Orbital) energy level of the electron transport layer. The "charge carrying component" is the material responsible for the LUMO energy level that actually transports electrons. This component may be the base material, or it may be a dopant. The LUMO energy level of an organic material may be generally characterized by the electron affinity of that material and the relative electron injection efficiency of a cathode may be generally characterized in terms of the work function of the cathode material. This means that the preferred properties of an electron transport layer and the adjacent cathode may be specified in terms of the electron affinity of the charge carrying component of the ETL and the work function of the cathode material. In particular, so as to achieve high electron injection efficiency, the work function of the cathode material is preferably not greater than the electron affinity of the charge carrying component of the electron transport layer by more than about 0.75 eV, more preferably, by not more than about 0.5 eV. Similar considerations apply to any layer into which electrons are being injected.
[0125] Cathode 160 may be any suitable material or combination of materials known to the art, such that cathode 160 is capable of conducting electrons and injecting them into the organic layers of device 100. Cathode 160 may be transparent or opaque, and may be reflective. Metals and metal oxides are examples of suitable cathode materials. Cathode 160 may be a single layer, or may have a compound structure. Figure 1 shows a compound cathode 160 having a thin metal layer 162 and a thicker conductive metal oxide layer 164. In a compound cathode, preferred materials for the thicker layer 164 include ITO, IZO, and other materials known to the art. U.S. Patent Nos. 5,703,436, 5,707,745, 6,548,956 B2, and 6,576,134 B2, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The part of cathode 160 that is in contact with the underlying organic layer, whether it is a single layer cathode 160, the thin metal layer 162 of a compound cathode, or some other part, is preferably made of a material having a work function lower than about 4 eV (a "low work function material"). Other cathode materials and structures may be used. [0126] Blocking layers may be used to reduce the number of charge carriers
(electrons or holes) and / or excitons that leave the emissive layer. An electron blocking layer 130 may be disposed between emissive layer 135 and the hole transport layer 125, to block elecfrons from leaving emissive layer 135 in the direction of hole transport layer 125. Similarly, a hole blocking layer 140 may be disposed between emissive layerl35 and electron transport layer 145, to block holes from leaving emissive layer 135 in the direction of electron transport layer 145. Blocking layers may also be used to block excitons from diffusing out of the emissive layer. The theory and use of blocking layers is described in more detail in United States Patent No. 6,097,147 and United States Patent Application Publication No. 2003-0230980 to Forrest et al., which are incorporated by reference in their entireties.
[0127] As used herein, and as would be understood by one skilled in the art, the term
"blocking layer" means that the layer provides a barrier that significantly inhibits transport of charge carriers and/or excitons through the device, without suggesting that the layer necessarily completely blocks the charge carriers and/or excitons. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.
[0128] Generally, injection layers are comprised of a material that may improve the injection of charge carriers from one layer, such as an electrode or an organic layer, into an adjacent organic layer. Injection layers may also perform a charge transport function. In device 100, hole injection layer 120 may be any layer that improves the injection of holes from anode 115 into hole transport layer 125. CuPc is an example of a material that may be used as a hole injection layer from an ITO anode 115, and other anodes. In device 100, electron injection layer 150 may be any layer that improves the injection of electrons into electron transport layer 145. LiF / Al is an example of a material that may be used as an electron injection layer into an electron transport layer from an adjacent layer. Other materials or combinations of materials may be used for injection layers. Depending upon the configuration of a particular device, injection layers may be disposed at locations different than those shown in device 100. More examples of injection layers are provided in U.S. Patent Application Serial No. 09/931,948 to Lu et al., which is incorporated by reference in its entirety. A hole injection layer may comprise a solution deposited material, such as a spin-coated polymer, e.g., PEDOT:PSS, or it may be a vapor deposited small molecule material, e.g., CuPc or MTDATA.
[0129] A hole injection layer (HIL) may planarize or wet the anode surface so as to provide efficient hole injection from the anode into the hole injecting material. A hole injection layer may also have a charge carrying component having HOMO (Highest Occupied Molecular Orbital) energy levels that favorably match up, as defined by their herein-described relative ionization potential (IP) energies, with the adjacent anode layer on one side of the HIL and the hole transporting layer on the opposite side of the HIL. The "charge carrying component" is the material responsible for the HOMO energy level that actually transports holes. This component may be the base material of the HIL, or it may be a dopant. Using a doped HIL allows the dopant to be selected for its electrical properties, and the host to be selected for morphological properties such as wetting, flexibility, toughness, etc. Preferred properties for the HIL material are such that holes can be efficiently injected from the anode into the HIL material. In particular, the charge carrying component of the HIL preferably has an IP not more than about 0.7 eV greater that the IP of the anode material. More preferably, the charge carrying component has an IP not more than about 0.5 eV greater than the anode material. Similar considerations apply to any layer into which holes are being injected. HIL materials are further distinguished from conventional hole transporting materials that are typically used in the hole transporting layer of an OLED in that such HIL materials may have a hole conductivity that is substantially less than the hole conductivity of conventional hole transporting materials. The thickness of the HIL of the present invention may be thick enough to help planarize or wet the surface of the anode layer. For example, an HIL thickness of as little as 10 nm may be acceptable for a very smooth anode surface. However, since anode surfaces tend to be very rough, a thickness for the HIL of up to 50 nm may be desired in some cases.
[0130] A protective layer may be used to protect underlying layers during subsequent fabrication processes. For example, the processes used to fabricate metal or metal oxide top electrodes may damage organic layers, and a protective layer may be used to reduce or eliminate such damage. In device 100, protective layer 155 may reduce damage to underlying organic layers during the fabrication of cathode 160. Preferably, a protective layer has a high carrier mobility for the type of carrier that it transports (electrons in device 100), such that it does not significantly increase the operating voltage of device 100. CuPc, BCP, and various metal phthalocyanines are examples of materials that may be used in protective layers. Other materials or combinations of materials may be used. The thickness of protective layer 155 is preferably thick enough that there is little or no damage to underlying layers due to fabrication processes that occur after organic protective layer 160 is deposited, yet not so thick as to significantly increase the operating voltage of device 100. Protective layer 155 may be doped to increase its conductivity. For example, a CuPc or BCP protective layer 160 may be doped with Li. A more detailed description of protective layers may be found in U.S. Patent Application Serial No. 09/931,948 to Lu et al., which is incorporated by reference in its entirety.
[0131] Figure 2 shows an inverted OLED 200. The device includes a substrate 210, an cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. Figure 2 provides one example of how some layers may be omitted from the structure of device 100.
[0132] The simple layered structure illustrated in Figures 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to Figures 1 and 2.
[0133] Structures and materials not specifically described may also be used, such as
OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190, Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be- used. OLEDs may be stacked, for example as described in U.S. Patent No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in Figures 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Patent No. 6,091,195 to Forrest et al., and / or a pit structure as described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties. [0134] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Patent No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Patent Application No. 10/233,470, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Patent Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink- jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
[0135] The molecules disclosed herein may be substituted in a number of different ways without departing from the scope of the invention. For example, substituents maybe added to a compound having three bidentate ligands, such that after the substituents are added, one or more of the bidentate ligands are linked together to form, for example, a tetradentate or hexadentate ligand. Other such linkages may be formed. It is believed that this type of linking may increase stability relative to a similar compound without linking, due to what is generally understood in the art as a "chelating effect."
[0136] Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, lights for interior or exterior illumination and / or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C to 30 degrees C, and more preferably at room temperature (20 - 25 degrees C). [0137] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures. [0138] As used herein, the term "carbene" refers to compounds having a divalent carbon atom with only six electrons in its valence shell when not coordinated to a metal. A useful exercise to determine whether a ligand includes a carbene-metal bond is to mentally deconstruct the complex as a metal fragment and a ligand, and to then determine whether a carbon atom in the ligand that was previously bound to the metal is a neutral divalent carbon atom in the deconstructed state. The resonance forms of a preferred embodiment may be shown as:
Figure imgf000028_0001
[0139] In the figures and structures herein, a carbene-metal bond may be depicted as
C→M, as for example:
Figure imgf000028_0002
[0140] Such structures that use an arrow to represent the presence of a metal-carbene bond are used interchangeably herein with structures that do not include the arrow, without any intention of suggesting there is a difference in the structure shown. [0141] This definition of carbene is not limited to metal-carbene complexes synthesized from carbenes, but is rather intended to address the orbital structure and electron distribution associated with the carbon atom that is bound to the metal. The definition recognizes that the "carbene" may not technically be divalent when bound to the metal, but it would be divalent if it were detached from the metal. Although many such compounds are synthesized by first synthesizing a carbene and then binding it to a metal, the definition is intended to encompass compounds synthesized by other methods that have a similar orbital structure and electron configuration. Lowry & Richardson, Mechanism and Theory in Organic Chemistry 256 (Harper & Row, 1976) defines "carbene" in a way that is consistent with the way the term is used herein. Some references may define "carbene" as a carbon ligand that forms a double bond to a metal. While this definition is not being used in the present application, there may be some overlap between the two definitions. A variety of representations are used to depict the bonding in such carbenes, including those in which a curved line is used to indicate partial multiple bonding between the carbene carbon and the adjacent heteroatom(s).
[0142] A compound comprising a carbene ligand bound to a metal center is provided.
Carbene compounds include small molecules, dendrimers, and polymers that include a carbene-metal bond. In one embodiment, the compound is a phosphorescent emissive material, preferably a dopant. The compound may also be doped into a wide band gap host material such as disclosed in U.S. Pat. Application No. 10/680,066, which is incorporated by reference in its entirety, or it may be doped into an inert wide band gap host such as disclosed in WO-074015, which is incorporated by reference in its entirety.
[0143] Embodiments of the present invention include metal-carbene compounds as high energy host materials. Such materials may be most useful for doped blue and green devices. The dopant in this case could be a triplet emitter or a singlet emitter (using phosphor sensitized fluorescence). In some embodiments, the dopant is a blue or UV emissive material. In this case, the host material preferably has a wide energy gap. As used herein, the energy gap refers to the difference in the energy between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) for a particular compound. The triplet energy for a given material is related to, but less than, the energy gap. Materials for use as a wide gap host are selected to have a wide energy gap so that the host material does not quench the dopant emission by endothermic or exothermic energy transfer. The wide gap host is preferably selected so as to have a triplet energy at least about 300 mV higher than that of the dopant. [0144] Additionally, the high band gap of metal-carbene compounds may make these materials effective in carrier blocking and transporting layers. Specifically, these materials may be used in the electron blocking layer, hole blocking layer, exciton blocking layer, hole transport layer, or electron transport layer of an OLED. In other embodiments a metal- carbene compound may be used as a hole injection layer, electron injection layer, or protective layer. It is believed that metal-carbene compounds described herein have improved thermal stability when incorporated into an organic light emitting device due to the carbene-metal bond, as compared to existing compounds without a carbene-metal bond. [0145] Carbene ligands are especially desirable in OLED applications due to the high thermal stability exhibited by metal-carbene complexes. It is believed that the carbene, which behaves much as an electron donative group, generally bonds strongly to the metals, thus forming a more thermally stable complex than, for example, previous cyclometallated complexes used as phosphorescent emitters. It is also believed that carbene analogs of ligands employed in existing phosphorescent emissive materials (for example the phenylpyridine or Irppy, etc.) may exhibit greater stability and emit at substantially higher energy than their existing analogs.
[0146] As used herein, a "non-carbene analog" of a metal carbene compound refers to existing ligands having a substantially similar chemical structure to the metal-carbene compound, but unlike the carbene compounds of the present invention, which features a carbene-metal bond, the analog has some other bond, such as a carbon-metal or a nitrogen- metal bond, in place of the carbene-metal bond. For example, Ir(ppz)3 has a nitrogen in each ligand bound to the Ir. Ir(l-phenylimidazolin-2-ylidene) is analogous to Ir(ppz)3 where the nitrogen bound to the Ir has been replaced with a carbene bound to the Ir, and where the atoms surrounding the carbene have been changed to make the carbon a carbene. Thus, embodiments of the present invention include metal-carbene complexes (e.g. Ir(l- phenylimidazolin-2-ylidene) with similar structures to existing emissive compounds (e.g. Ir(ppz)3).
[0147] Examples of existing emissive compounds include Ir(ppy)3 and Ir(ppz)3, discussed above. Other examples are disclosed in the references below, which are incorporated herein by reference in their entirety. In preferred embodiments, the carbene ligands are imidazoles, pyrazoles, benzimidazoles, and pyrroles.
[0148] It is believed that the carbene-metal bond in Ir(l-Ph-3-Me-imid)3 is stronger than the N-metal bond in rr ppz)3. Moreover, due to the nature of a carbene-metal bond, it is believed that replacing a carbon-metal bond or nitrogen-metal bond in existing emissive organometallic molecules with a carbene-metal bond (making other changes as needed to make the carbon atom a carbene) may result in an emissive molecule that is more stable than the non-carbene analog, and that has stronger spin-orbit coupling. It is further believed that the emissive spectra of the molecule including a carbene may be different from the emissive spectra of the analog without a carbene.
[0149] Metal-carbene complexes may be tuned to emit a wide variety of spectra from the near-ultraviolet across the entire visible spectra by the selection of substituents and/or chemical groups on the ligand(s). More significantly, it may now be possible to obtain saturated blue color emissions with peak wavelengths at about 450 nm. Because it is believed to be materially easier to reduce than to increase the triplet energy by tuning an emissive compound, the ability to make stable blue emitters at such high energies would also allow for the possibility of obtaining any color by reducing the energy so as to red-shift the emission. For example, Fig. 18 shows that Ir(l-Ph-3-Me-imid)3, which is a preferred embodiment of this invention, in a 2-MeTHF solution emits in the near-UV spectra at a wavelength of about 380 nm at 77 K and at room temperature. The substitution of a fluorenyl group for the phenyl group attached to the methylimidazole results in a red-shift in the emission as shown in Fig. 26. Thus, Fig. 26 shows Ir-(FlMeImid)3, which is another embodiment of this invention, to emit at the visible part of the spectra at a wavelength of 462 nm at 77 K and at 466 nm at room temperature.
[0150] The appropriate selection of substituents and/or chemical groups attached to carbene ligands may also minimize quantum efficiency losses associated with increasing temperatures. The observable difference in lifetime measurements between emission at room temperature and at low temperatures (e.g. 77 K) is believed to be attributed to non-radiative quenching mechanisms that compete with phosphorescent emission. Such quenching mechanisms are further believed to be thermally activated, and consequently, at cooler temperatures of about 77 K, where energy loss due to quenching is not an issue, quantum efficiency is about 100%). For example, Fig. 21 shows the emission spectra of fac-Ir(l-Ph-3- Me-imid)3 in 2-MeTHF. The compound exhibits a lifetime of 6.8 μs at 77 K and 0.50 μs at room temperature, and the difference may be attributed to quenching mechanisms. It is believed that appropriate substituents on the carbene ligand, or doping in a more rigid matrix, such as disclosed in Turro, "Modern Molecular Photochemistry", University Science Books (1991), 109-10, may increase quantum efficiency at room temperature and correspondingly show longer lifetimes.
[0151] Due to the nature of the carbene-metal bond, the emission of a carbene analog may be substantially different from that of its non-carbene analog, and the emission of the carbene analog may be stable and at a higher energy than previously obtainable with stable non-carbene compounds. Embodiments of the present invention shown in Figs. 18, 21, 25, and 26, show higher energy emissions than have previously been obtained with other phosphorescent organometallic emissive materials. It is believed that devices incorporating these materials, and having optimized architecture, will have electroluminescent spectras showing high triplet energies similar to the photoluminescent spectras shown in these figures. [0152] In some embodiments, the triplet energy of the carbene complex has a corresponding wavelength in the deep blue or ultraviolet (UV) part of the spectra. In some embodiments, the phosphorescent emissive compound has triplet energy corresponding to a wavelength of less than 450 nm. h preferred embodiments, the triplet energy corresponds to a wavelength of less than 440 nm, and in even more preferred embodiments, it corresponds to a wavelength less than 400 nm, which is believed to be in the UV region of the spectrum, since 400 nm is believed to represent the cut-off between the UV and the visible regions of the spectrum. Such high triplet energy may make these compounds useful in optically pumping down converting layers. For such applications, an overlap is preferred between the emission spectra of the ultraviolet carbene compound and the absorption spectra of the down converting layer. It is believed that when about 50 % of the integral of the curve for the normalized electroluminescent spectra of the device is at a wavelength less than about 450 nm, there is sufficient energy to optically pump a down converting layer. More preferably, greater than 90 % of the emission may be produced below 440 nm, as disclosed herein. Preferably, 50 % of the integral of the curve for the normalized electroluminescent spectra is less than about 440 nm, and more preferably, it is less than about 400 nm. The wavelength cutoffs mentioned above are not intended to be absolute limitations as they depend on the energy of the material to be pumped. It is also believed that these emissions may occur at room temperature.
[0153] The strong metal-carbon bond is also believed to lead to greater spin-orbit coupling in metal carbene complexes. Moreover, the triplet energy of coordinated carbenes are shown to be significantly higher than pyridine analogs. Fig. 18 shows the emission spectra of mer-Ir(l-Ph-3-Me-imid)3, which is one of the embodiments of the invention. The emission is shown to be in the near-ultraviolet range of the spectrum even at room temperature. It is believed herein that other metal carbene complexes may be capable of emitting at similarly high energies due to the strong metal-ligand bond associated with carbene ligands.
[0154] The stability of metal-carbene complexes may also allow increased versatility in the types of ligands and metals that may be used as phosphorescent emitters in OLEDs. The strong metal- carbene bond may allow a variety of metals to form useful phosphorescent complexes with carbene ligands to give novel emissive compounds. For example, one embodiment includes gold or copper bonded to a carbene ligand. Such metals have been calculated to form metal-carbon bonds having quite high bond dissociation energies, such as illustrated in Nemcsok et al., "The Significance ofπ-Interactions in Group 11 Complexes with N-Heterocyclic Carbenes " xxxx American Chemical Society, Publ. on Web, 06/19/2004. Such high bond dissociation energies may be expected to improve the chemical stability of metal-carbene complexes as compared with the analogous metal-phenyl-pyridine ("metal- ppy") based complexes that are typically used in an OLED. Thus, in addition to their use as the emissive materials in an OLED, metal-carbene complexes may be also used advantageously, because of their improved chemical stability, for other functions in an OLED, for example, as a host material in the emissive layer, as an electron or hole transporting material in an electron or hole transporting layer, and/or as an electron or hole blocking material in an electron or hole blocking layer.
[0155] Additionally, although cyclometallated complexes are preferred embodiments, the present invention is not limited to such embodiments. The increased strength of a metal- carbene bond, as compared to other types of bonds with metal, may make monodentate ligands feasible for use as emissive materials. Until recently, bidentate ligands were sfrongly preferred due to stability concerns. Thus, embodiments include monodentate carbene ligands as well as bidentate. Embodiments also include tridentate carbene ligands, which may be quite stable, and many examples are found in the art, such as those disclosed in Koizumi et al., Organometallics 2003, 22, 970-975. Other embodiments may also feature a tetradentate ligand, such as porphyrin analogs in which one or more nitrogens are replaced by a carbene, which is disclosed in Bourissou et al. Chem Rev. 2000, 100, 39-91. Still other embodiments may include metallaquinone carbenes, which are compounds in which one of the oxygen atoms of a quinone has been replaced by a metal, such as those disclosed in Ashekenazi et al., J. Am. Chem. Soc. 2000, 122, 8797-8798. In addition, The metal-carbene compound maybe present as part of a multi-dentate group such as disclosed in U.S. Pat. Application No. 10/771,423 to Ma et al., which is incorporated by reference in its entirety. [0156] It is believed that many of the (C,C) or (C,N) ligands of many existing electroluminescent compounds maybe modified to create an analogous (C,C) ligand including a carbene. Specific non limiting examples of such modification include: (1) the substituents on the carbene-bonded branch of the (C,C)-ligand and the substituents on the mono-anionic-carbon-bonded branch of the (C,C)-ligand may be independently selected from the group consisting of (a) the substituents on the N-bonded branch of the existing (C,N)-ligands, such as disclosed in the references listed below, which is typically but not necessarily a pyridine group; and (b) the substituents on the mono-anionic-carbon-bonded branch of the existing (C,N)-ligands, such as disclosed in the references listed below, which is typically but not necessarily a phenyl group; (c) and/or a combination thereof; and (2) the compounds including the metal-carbene bonds may further include ancillary ligands selected from the group consisting of the ancillary ligands such as disclosed in the following references:
U.S. Pat. Application Publ. No. 2002-0034656 (K&K 10020/15303), Figs. 11-50, U.S. Pat. Application Publ. No. 2003-0072964 (Thompson et al), paragraphs 7-132; and Figs. 1-8; U.S. Pat. Application Publ. No. 2002-0182441 (Lamansky et al.), , paragraphs 13-165, including Figs. l-9(g); U.S. Pat. No. 6,420,057 Bl (Ueda et al.), col. 1, line 57, through col. 88, line 17, including each compound 1-1 through XXIV-12; U.S. Pat. No. 6,383,666 Bl (Kim et al.), col. 2, line 9, through col. 21, lin3 67; U.S. Pat. Application Publ. No. 2001- 0015432 Al (Igarashi et al.), paragraphs 2-57, including compounds (1-1) through (1-30); U.S. Pat. Application Publ. No. 2001-0019782 Al (Igarashi et al.), paragraphs 13- 126, including compounds (1-1) through (1-70), and (2-1) through (2-20); U.S. Pat. Application Publ. No. 2002-0024293 (Igarashi et al.), paragraphs 7-95, including general formulas K-I through K-VI, and example compounds (K-l) through (K-25); U.S. Pat. Application Publ. No. 2002-0048689 Al (Igarashi et al.), paragraphs 5-134, including compounds 1-81, and example compounds (1-1) through (1-81); U.S. Pat. Application Publ. No. 2002-0063516 (Tsuboyama et al.), paragraphs 31-161, including each compound 1-16; U.S. Pat. Application Publ. No. 2003-0068536 (Tsuboyama et al.), paragraphs 31-168, including each compound in Tables 1-17, corresponds to EP-1-239-526-A2; U.S. Pat. Application Publ. No. 2003- 0091862 (Tokito et al.), paragraphs 10-190, including each compound in Tables 1-17, corresponds to EP-1-239-526-A2; U.S. Pat. Application Publ. No. 2003-0096138 (Lecloux et al.), paragraphs 8-124, including Figs. 1-5; U.S. Pat. Application Publ. No. 2002-0190250 (Grushin et al), paragraphs 9-191; U.S. Pat. Application Publ. No. 2002-0121638 (Grushin et al.), paragraphs 8-125; U.S. Pat. Application Publ. No. 2003-0068526 (Kamatani et al.), paragraphs 33-572, including each compound in Tables 1-23; U.S. Pat. Application Publ. No. 2003-0141809 (Furugori et al.), paragraphs 29-207; U.S. Pat. Application Publ. No. 2003- 0162299 Al (Hsieh et al.), paragraphs 8-42; WO 03/084972, (Stossel et al.), Examples 1-33; WO 02/02714 A2 ((Petrov et al), pages 2-30, including each compound in Tables 1-5; EP 1- 191-613 Al(Takiguchi et al.), paragraphs 26-87, including each compound in Tables 1-8, (corresponding to U.S. Pat. Application Publ. No. 2002-0064681); and EP 1-191-614 A2 (Tsuboyama et al.), paragraphs 25-86, including each compound in Tables 1-7; which are incorporated herein by reference in their entirety.
[0157] Carbene ligands may be synthesized using methods known in the art, such as those disclosed in Cattoen, et al., J. Am. Chem. Soc, 2004, 126; 1342-1343; Chiu-Yuen Wong, et al, Organometallics 2004, 23, 2263-2272; Klapars, et al, J. Am. Chem. Soc, 2001, 123; 7727-7729; Bourissou et al. Chem Rev. 2000, 100,39-91; Siu-Wai Lai, et al, Organometallics 1999, 18, 3327-3336; Wen-Mei Xue et al, Organometallics 1998, 17, 1622- 1630; Wang & Lin, Organometallics 1998, 17, 972-975; Cardin, et al, Chem Rev. 1972, 5, 545-574; and other references discussed herein.
[0158] In one embodiment, a phosphorescent emissive compound having the following formula is provided: z2 X - wherein Z and Z may be a carbon containing moiety, an amine containing moiety, oxygen containing moiety, a phosphine containing moiety, and a sulfur containing moiety.
[0159] In another embodiment, the compound has the structure:
Figure imgf000035_0001
in which the ligands have the structure:
Figure imgf000036_0001
in which
M is a metal; the dotted lines represent optional double bonds; each Zi, A, and A' is independently selected from C, N, O, P, or S;
Ri, R2, and R3 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl,
CN, CF3 C(O)OR', C(O)R\ C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R',
CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6- membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl;
(X-Y) is selected from a photoactive ligand or an ancillary ligand, α is O, 1, or 2. m is a value from 1 to the maximum number of ligands that may be attached to the metal; m + n is the maximum number of ligands that may be attached to metal M.
[0160] The term "halo" or "halogen" as used herein includes fluorine, chlorine, bromine and iodine.
[0161] The term "alkyl" as used herein contemplates both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Additionally, the alkyl group may be optionally substituted with one or more substituents selected from halo, CN, CO2R, C(O)R, NR2, cyclic-amino, NO2, and OR, wherein each R is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl. [0162] The term "cycloalkyl" as used herein contemplates cyclic alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 7 carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, and the like. Additionally, the cycloalkyl group may be optionally substituted with one or more substituents selected from halo, CN, CO2R, C(O)R, NR2, cyclic-amino, NO2, and OR.
[0163] The term "alkenyl" as used herein contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl group may be optionally substituted with one or more substituents selected from halo, CN, CO2R, C(O)R, NR2, cyclic-amino, NO2, and OR. [0164] The term "alkynyl" as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted with one or more substituents selected from halo, CN, CO2R, C(O)R, NR2, cyclic-amino, NO2, and OR. [0165] The terms "aralkyl" as used herein contemplates an alkyl group that has as a substituent an aromatic group. Additionally, the aralkyl group may be optionally substituted on the aryl with one or more substituents selected from halo, CN, CO2R, C(O)R, NR2, cyclic-amino, NO2, and OR.
[0166] The term "heterocyclic group" as used herein contemplates non- aromatic cyclic radicals. Preferred heterocyclic groups are those containing 3 or 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperdino, pyrrolidino, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like. Additionally, the heterocyclic group may be optionally substituted with one or more substituents selected from halo, CN, CO R, C(O)R, NR2, cyclic- amino, NO2, and OR,
[0167] he term "aryl" or "aromatic group" as used herein contemplates single-ring groups and polycyclic ring systems. The polycyclic rings may have two or more rings in which two carbons are common by two adjoining rings (the rings are "fused") wherein at least one of the rings is aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles and/or heteroaryls. Additionally, the aryl group may be optionally substituted with one or more substituents selected from halo, CN, CO2R, C(O)R, NR2, cyclic-amino, NO2, and OR,
[0168] The term "heteroaryl" as used herein contemplates single-ring hetero- aromatic groups that may include from one to three heteroatoms, for example, pyrrole, furan, thiophene, imidazoie, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine and pyrimidine, and the like. The term heteroaryl also includes polycyclic hetero-aromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings are "fused") wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles and/or heteroaryls. Additionally, the heteroaryl group may be optionally substituted with one or more substituents selected from halo, CN, CO2R, C(O)R, NR2, cyclic-amino, NO2, and OR.
[0169] All value ranges, for example those given for n and m, are inclusive over the entire range. Thus, for example, a range between 0-4 would include the values 0, 1, 2, 3 and 4.
[0170] Embodiments include photoactive carbene ligands. m represents the number of photoactive ligands. For example, for Ir, m may be 1, 2 or 3. n, the number of "ancillary" ligands of a particular type, may be any integer from zero to one less than the maximum number of ligands that may be attached to the metal. (X-Y) represents an ancillary ligand. For example, for Ir, n may be 0, 1 or 2 for bidentate ligands. Ancillary ligands for use in the emissive material may be selected from those known in the art. Non-limiting examples of ancillary ligands may be found in PCT Application Publication WO 02/15645 Al to Lamansky et al. at pages 89-90, which is incorporated herein by reference. [0171] The metal forming the metal-carbene bond may be selected from a wide range of metals. Preferred metals include main group metals, 1st row transition metals, 2n row transition metals, 3rd row transition metals, and lanthanides. Although one skilled in the art typically expects room temperature phosphorescence only from metal atoms that exert a strong heavy atom effect, phosphorescent emission has been observed in Kunkley, et al. J. Organometallic Chem. 2003, 684, 113-116 for a compound with a Nickel (Ni) metal, which is typically not expected to exert a strong heavy atom effect. Thus, embodiments also include first row transition metal, such as Ni, and other metals that do not normally exert a strong heavy atom effect but exhibits phosphorescent emission when coordinated to one or more carbene ligands. More preferred metals include 3r row transition metals. The following are also preferred metals: Ir, Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag. Most preferably, the metal is Iridium.
[0172] The most preferred embodiments are N-heterocyclic carbenes, which
Bourissou has also reported as having "remarkable stability" as free compounds in Bourissou et al. Chem Rev. 2000, 100, 39-91. [0173] In one embodiment, the metal-carbene compound has the structure
and the ligand has the structure
Figure imgf000039_0001
in which i is either an aromatic or an amine group; and R3 and R4 together from independently a 5 or 6-member cyclic group, which may be cycloalkyl, cycloheteroalkyl, aryl or heteroaryl, and which may optionally be substituted by one or more substituents J. [0174] In other embodiments, the metal-carbene compound may have one of the following structures
Figure imgf000039_0002
in which the ligand has the corresponding structure selected from:
Figure imgf000039_0003
in which R5 and R6 may be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; and additionally or alternatively, one or more of Ri and R2, R2 and R3, R3 and R5, and R5 and R6 together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J.
[0175] In another embodiment the metal carbene compound has the structure:
and the carbene ligand has the structu
Figure imgf000040_0001
re in which R8, R , R10, and Rπ may be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3
C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl;and additionally or alternatively, one or more of Ri and R2, R2 and R8, R8 and R10, and R6 and R10 together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J.
[0176] In another embodiment, the carbene-metal compound may have one of the structures below:
Figure imgf000040_0002
in which the ligand has the structure selected from
Figure imgf000041_0001
and in which each R12 maybe hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R1 groups on adjacent ring atoms may form a fused 5- or 6-membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; and d is 0, 1 , 2, 3 , or 4. [00100] Another embodiment has a metal-carbene structure:
with a ligand having the structure
Figure imgf000041_0002
R13 may be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' may be halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R13 groups on adjacent ring atoms may form a fused 5- or 6-membered cyclic group, in which the cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and which is optionally substituted by one or more substituents J; and c may be 0, 1, 2, or 3. [0177] In most preferred embodiments, the compound includes a carbene ligand coordinated to a metal center where at least one carbene ligand includes a nitrogen containing heterocyclic ring. Preferred compounds include:
Figure imgf000042_0001
in which the corresponding ligands have the structures
Figure imgf000042_0002
in which Z3 is independently selected from the group consisting of a C, O, S, P, or NR'; ring B is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M, wherein ring B can be optionally substituted with one or more substituents R14; and ring D is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M, wherein ring D can be optionally substituted with one or more substituents R15; and R14 and R15 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SiR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R groups on the same or adjacent ring atoms form a fused 5- or 6-membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; b is 0, 1, 2, 3, or 4. 8] Preferred compounds have the structure:
Figure imgf000043_0001
and the corresponding ligand has the structure:
Figure imgf000043_0002
Figure imgf000043_0003
More preferably the metal-carbene has a structure:
Figure imgf000044_0001
Figure imgf000045_0001
[0180] Another preferred embodiment has the structure:
Figure imgf000045_0002
ligand has the structure
Figure imgf000045_0003
in which R6 is an alkyl or aryl group. In a most preferred embodiment, the metal is Ir. Preferably, m is 3 and n is 0. In one embodiment, R6 is methyl. In another embodiment m is 2 and n is one. The ancillary ligand X-Y may have one of the following structures:
Figure imgf000045_0004
[0181] Other preferred ancillary ligands are acetylacetonate, picolinate, and their derivatives.
[0182] Other preferred embodiments have the following general structures:
Figure imgf000045_0005
Figure imgf000045_0006
Figure imgf000046_0001
ve the structure
Figure imgf000046_0002
Figure imgf000047_0001
More preferred embodiments have the following structures:
Figure imgf000047_0002
Figure imgf000048_0001
Al
Figure imgf000049_0001
and more preferred ligands have the following corresponding structures
Figure imgf000049_0002
Figure imgf000050_0001
Figure imgf000050_0002
Figure imgf000051_0001
[0183] In another embodiment, the carbene compound includes a triazole ring coordinated to a metal. In a preferred embodiment, the compound has the structure:
Figure imgf000051_0002
and the ligands may have the
corresponding structure
Figure imgf000051_0003
and
Preferably, the metal-carbene compound has the structure:
Figure imgf000051_0004
carbene ligand has the structure
Figure imgf000052_0001
] Other preferred embodiments include:
Figure imgf000052_0003
which the ligands have the structure
Figure imgf000052_0004
Figure imgf000053_0001
[0185] More preferably the triazole carbene compound has the structure:
Figure imgf000053_0002
Dopant Q This embodiment includes a ligand with the structure:
Ligand Q
[0186] In another embodiment, the triazole carbene compound has the structure:
Figure imgf000053_0004
This embodiment includes a ligand with the structure:
Figure imgf000054_0001
[0187] In another embodiment, the carbene compound includes a tefrazole ring coordinated to a metal. In a preferred embodiment, the compound has the structure:
Figure imgf000054_0002
in which the corresponding ligand has the structure:
Figure imgf000054_0003
[0188] Preferably, the compound has the structure:
Figure imgf000054_0004
an t e gan as t e structure: <R«)t
[0189] More preferably, the compound has the structure
Figure imgf000054_0005
and the ligand has the structure:
Figure imgf000054_0006
[0190] In another embodiment the compound has the structure: and the ligand has
Figure imgf000055_0001
wherein Z4 and Z5 are independently selected from a bond, O, S, or NR'; Zls A, A1? A', and
A" is independently selected from C, N, or P;
[0191] More preferred embodiments include compounds with the structure:
Figure imgf000055_0002
in which the ligands have the structure:
Figure imgf000055_0003
[0192] In other embodiments ligands with carbon donors can only be drawn with a zwitterionic resonance structure, and are hereinafter referred to as "zwitterionic carbon donors." It is possible to draw a resonance structure where the carbon coordinated to the metal center is a carbene as shown below.
Figure imgf000056_0001
[0193] Preferred compounds having zwitterionic carbon donor ligands include heterocyclic compounds comprising at least one nitrogen atom. Preferred compounds include:
Figure imgf000056_0002
[0194] Embodiments also include zwitterionic carbon donor ligands with the structure:
Figure imgf000057_0001
[0195] In some embodiments that include a zwitterionic carbon donor ligand, such as those depicted above, the carbon coordinated to the metal center is not directly bonded to a heteroatom.
[0196] Devices incorporating the above compounds have been shown to exhibit phosphorescent emissions that span the spectrum of blue light. For example, Dopant A and B, in Examples 31 and 32 respectively, are UV emitters in solution photoluminescence (PL) and the electroluminescence (EL) emission has a highest energy peak or shoulder at about 400 nm as shown in Figure 47. Dopants M, N, O, and P, in Examples 43, 44, 45 and 46 respectively, have slightly lower triplet energy and emit in a device with high efficiency using the wide band gap (high triplet energy) host, UGH5. These examples have similar triplet energy and the EL emission shows vibronic fine structure characteristic of the dopant. The emission from these examples is a desirable blue color with a CIE coordinate of about (0.14, 0.15).
[0197] Other devices, for example, the devices of Examples 38, 39 and 40 (Dopants
H, I, and J) exhibit emissions at lower energy with a highest triplet energy emission at about 470 nm and vibronic fine structure characteristic of the dopant (Figure 59). Examples 33 and 34 (Dopants C and D) exhibit still lower energy with highest energy emission at about 485 nm (Figure 50).
[0198] Other embodiments also include compounds having ancillary carbene ligands.
For example, the dopant in the device of Examples 13 and 14 is an Iridium compound having two photoactive phenylpyridine (ppy) ligands and one carbene ancillary ligand:
Figure imgf000058_0001
[0199] Embodiments also include carbene complexes useful as host materials in
OLEDs. These carbene complexes are believed to exhibit deep HOMO energy levels and high LUMO energy levels as compared, for example, to CBP, which is commonly used as a host material in OLEDs, while maintaining the high triplet energies and the wide energy gap required to energetically embed the dopant. In addition, it is believed that strategic placement of electron withdrawing groups or N-heterocycles, as exemplified by preferred embodiments, result in carbene complexes with increased oxidation potential suitable as host materials. [0200] In some embodiments, the host material comprises a compound having at least one carbene atom coordinated to iridium wherein the compound has the structure:
Figure imgf000058_0002
where the dotted lines represent optional double bonds; ring A may be an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to iridium, and ring A may be optionally substituted with one or more substituents Ra; RΪ may be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; R2-R5 may be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R or Ra groups on the same or adjacent ring, together may form independently a 5 or 6-member cyclic group, which may be a cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group may be substituted by one or more substituents J; each substituent J may be R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms may form a fused 5- or 6-membered aromatic group; each R' may be halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; and b is 0, 1, 2, or 3.
[0201] The corresponding ligand may have the structure:
Figure imgf000059_0001
In preferred embodiments, the host material includes a compound having the structure:
Figure imgf000059_0002
and corresponding ligands having the structure
Figure imgf000059_0003
[0202] Preferably, at least one of Rai and Ra3 is F. More preferred compounds include:
Figure imgf000059_0004
and the ligands include:
Figure imgf000060_0001
[0203] In another preferred embodiment, the host material comprises a carbene compound having the structure:
Figure imgf000060_0002
wherein ring B is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to iridium, wherein ring B may be optionally substituted with one or more substituents Rb; Rb maybe hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two Rb groups on the same ring, together may form independently a 5 or 6-member cyclic group, which may be a cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group may be substituted by one or more substituents J. [0204] Preferably the ligand has the structure:
Figure imgf000060_0003
[0205] In more preferred embodiments, the host material includes a carbene compound having the structure:
Figure imgf000061_0001
and carbene ligands having the structure
Figure imgf000061_0002
[00101] In a most preferred embodiment, the host material comprises a carbene compound with the structure:
Figure imgf000061_0003
Ir(bmi)3 For example, the host materials for the devices of Examples 51-54 comprise Ir(bmi)3. The high LUMO energy of the such host material is believed to allow for electron trapping on the dopant, which may lead to efficient charge recombination when holes are confined to the emissive layer. Figure 75 and Figure 78 show that devices that use HPT, which in addition to facilitating electron transport is also effective at blocking holes, exhibit higher quantum efficiency than comparable devices of Example 51 and 53. The higher quantum efficiency may be attributed to efficient recombination that occurs on the dopant and that the host material has a sufficiently high triplet energy to not quench emission from the dopant [0206] In a preferred embodiment, the ligand has the structure:
Figure imgf000062_0001
[0207] In another preferred embodiment, the host material comprises a carbene compound with the structure:
Figure imgf000062_0002
Preferably, the carbene ligand has the structure:
Figure imgf000062_0003
wherein, additionally or alternatively, R and Rai and two adjacent Ra groups on the same ring together form independently a 5 or 6-member cyclic group, which may be a cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group may be substituted by one or more substituents J.
[0208] More preferred embodiments include carbene compounds having the structure:
Figure imgf000063_0001
More preferred carbene ligands include:
Figure imgf000063_0002
[0209] In another embodiment, the host material comprises a carbene compound having the structure:
Figure imgf000063_0003
wherein ring C is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to Ir, wherein ring C can be optionally substituted with one or more substituents Re;
Re may be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2,
NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two Re groups on the same ring, together may form independently a 5 or 6-member cyclic group, which may be a cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group may be substituted by one or more substituents J.
[0210] Preferably, the carbene ligand has the structure:
Figure imgf000064_0001
[0211] In other preferred embodiments, the carbene compound has the structure:
Figure imgf000064_0002
Other preferred ligands include:
Figure imgf000064_0003
[0212] As used herein, the term "redox active metal" refers to a metal in a complex, i.e., a metal ion surrounded by ligands, that can undergo reduction or oxidation. For the metal to be "redox active," oxidation and reduction of the complex occur principally at the metal center, and not on the ligands complexed to the metal. As a result, the oxidation state of the metal changes upon reduction or oxidation of the complex, such that the electronic density on the ligands remains substantially unchanged, and the ligands, typically, do not dissociate from the complex.
[0213] As used herein, the term "redox active reducible metal complex" refers to a metal complex, as described above, where the metal is capable of oxidation and reduction in an electrochemical process. For example, for a metal complex of formula TiX}, where X is anionic ligand, the Ti is in the 4+ oxidation state, i.e., Ti(IV) or Ti4+. Upon reduction, an electron is added to the complex, and the complex takes a negative charge, i.e., TiXf, and the Ti is reduced to its 3+ oxidation state, i.e., Ti(III) or Ti3+. As discussed above, the electron added in the reduction process is primarily located on the Ti center of the reduced complex. [0214] As used herein, the term "readily switch redox state" refers to a metal complex in a first redox state that can readily switch to a second, accessible redox state at a moderate potential. As will be understood by those of skill in the art, the redox state of a complex is a function of the number of electrons in the complex, which changes when the complex is reduced or oxidized. For a neutral complex, oxidation or reduction in a series of single steps, adding (reduction) or removing (oxidation) electrons, takes the complex through a series of redox states. When a neutral complex is reduced, the complex gains a negative charge, which increases with each successive reduction. Oxidation of a reduced complex reverses the process. If the voltage required to remove or add electrons to a complex is moderate, the redox state can be switched readily. If the energy required to shift between redox states is high, the state will not be switched readily. In addition, a high kinetic barrier may exist for a change in redox state. As a result, the voltage required for the change in state must be accessible in the matrix or solvent containing the complex, and the kinetic barrier to the redox reaction must be a small for the complex to readily switch redox state. In addition, the kinetic barriers to electron transfer can be minimized by a careful selection of a metal that has a low reorganization barrier to electron transfer. The kinetic barriers for reduction of metal complexes are best described by Marcus electron transfer theory.
[0215] As used herein, the term "resting state" refers to the neutral state of a vacuum deposited device. More generally, the resting state is the redox state of a complex before any charge is injected. For solution processed OLEDs, where the complex is initially in the form of a cation, the cation is the resting state, and the neutral form of the complex carries the elecfron.
[0216] Preferably, an OLED in accordance with the invention has at least one organic layer comprising a reversibly reducible metal complex with a redox active metal. This complex may be used in the device at least as an ETL or as a host material. The preferred reversibly reducible metal complexes readily undergo a reversible change of oxidation state, and, thus, may be referred to as reversibly reducible metal complexes. That is, for example, for a reversibly reducible metal complex comprising Ti(IV) as the metal, the Ti(IV) may be reduced to Ti(III) in the complex without the dissociation of a ligand, and then oxidized to Ti(IV). This process allows for the transport of electrons through the material. [0217] A preferred OLED of the invention comprises an anode; a cathode; and at least one organic layer disposed between the anode and the cathode. The organic layer comprises a reversibly reducible metal complex of a redox active metal center and at least one ligand, where, following a reduction of the complex that adds one extra electron to the complex, the extra electron is predominantly localized on the metal center of the reduced complex. That is, as will be recognized by those skilled in the art, substantially all of the charge of the electron will be on the metal, rather than on the ligands. The location of the electron in such a reduced complex may be determined with X-Ray Absorption Fine Structure ("XAFS") techniques, but is best determined through theoretical calculations, such as density function theory calculation (DFT), or Electron Paramagnetic Resonance ("EPR"). [0218] Preferably, the metal is a d(0) metal, such as Ti(IV). By using a d(0) metal with ligands having an inherently high π* energy level, the extra electron of the reduced species is localized on the metal center. The localization of the electron on the metal of a reduced metal complex prevents bond formation between two reduced complexes. It may also improve the stability of the complex, as the electron charge is not distributed on the ligands, where irreversible bond breakage could lead to decomposition. As discussed above, in all prior art electron transport materials, the electron added during reduction is predominantly in a ligand based orbital.
[0219] Useful ligands preferably contain two electron donors, such as carbenes, that form a coordinatively saturated metal center, and do not dissociate from the metal center upon reduction of the complex. Carbenes are particularly preferred, as carbenes are less likely to dissociate from the metal complex upon reduction of the complex, due to the strength of the carbene-metal bond. Particularly useful ligands include, but are not limited to:
Figure imgf000066_0001
Figure imgf000066_0003
Figure imgf000066_0002
Figure imgf000067_0001
where E1 and E3 are either/or nitrogen, oxygen, or sulfur mono anionic donors, E2 is a C, N, P, Si, etc neutral donor,
Figure imgf000068_0001
[0220] The reversibly reducible metal complexes useful in the invention are neutral and substantially colorless in the resting state, preferably having an extinction coefficient at wavelengths from about 400nm to about 750 nm in the resting state of no more than about 1000 M^-cm"1, and, more preferably, no more than about 100 M^-cm"1. Preferred reducible metal complexes in accordance with the invention are of Formula I
Figure imgf000069_0001
and Formula II
Figure imgf000069_0002
where Mi is a redox active transition metal, preferably a redox active dO transition metal; E1 and E3 are independently selected from nitrogen, oxygen, and sulfur mono-anionic donors; E2 is a C, N, P, or Si neutral donor; (X-Y) is selected from a photoactive ligand or an ancillary ligand; m is a value from 1 to the maximum number of ligands that maybe attached to metal Mi; and m + n is the maximum number of ligands that may be attached to metal Mi, such that the overall complex is neutral.
[0221] Particularly useful reversibly reducible metal complexes include, but are not limited to complexes of formula:
Figure imgf000069_0004
Figure imgf000069_0003
Figure imgf000070_0001
where E1 and E3 are either/or nitrogen, oxygen, or sulfur mono anionic donors, and E is a C, N, P, Si, or similar neutral donor,
Figure imgf000071_0002
Figure imgf000071_0001
[0222] In some embodiments, the metal-carbene complex is cationic. The cationic metal-carbene complex will have as positive charge ranging from 1+ to 6+, and preferably from 1 to 3 . The cationic metal-carbene complex will be associated with a counterion to balance the charge. The counterion may be selected from any appropriate anion which does not interfere with the function of the compound in the device, for example, as an emissive material. The anion is selected to be electrochemically inert over the operational voltage range of the device. Preferred counteranions are typically weakly coordinating anions. The term "weakly coordinating anion" is well known in the art per se and generally refers to a large bulky anion capable of delocalization of the negative change of the anion. Suitable weakly coordinating anions, not all of which would be considered bulky, include, but are not limited to: PF6 ", BF4 ", SbCl6 ", trifluoromethansulfonate, BAr4 " (Ar = C6F5), BAr'4 " (Ar' = 3,5- bis(trifluoromethyl)phenyl, and the like. The weakly coordinating nature of such anions is known to those skilled in the art and described in the literature (S. Strauss et al., Chem. Rev., 1993, 93, 927).
[0223] In embodiments where the metal-carbene complexes are cationic, the metal center, the carbene ligand(s), the optional ancillary ligand(s), and the optional additional photoactive ligand(s) are selected in combination so that the resulting metal complex has a positive charge.
[0224] In preferred embodiments, the cationic metal-carbene complex will be an emissive material. In a further preferred embodiment, the cationic metal-carbene complex will further comprise one or more carbon-metal bonds that are not carbene-metal bonds (i.e., a covalent carbon-metal bond). Particularly preferred is a phenyl bonded to the metal center, as it is believed that this type of bonding promotes relaxation, which may result in better emissive properties. Thus, in a preferred embodiment, the cationic metal-carbene complex will have at least one carbon-metal bond that is a carbene-metal bond and at least one carbon- metal bond that is a non-carbene carbon-metal bond, and preferably is a phenyl-metal bond. [0225] In a preferred embodiment, the emissive cationic metal-carbene complex emits in the blue region of the visible spectrum. The emissive cationic metal-carbene complex will preferably have an emission spectra with the λmax less than about 500 nm, and more preferable less than about 450 nm. In another preferred embodiment, the device comprising the cationic metal-carbene complex will emit light having CIE coordinates wherein the X-coordinate is from about 0.10 to about 0.15, and the Y-coordinate in from about 0.10 to about 0.20.
[0226] The embodiments of the cationic metal-carbene complexes will have associated therewith (i) a positive charge, and (ii) an anionic species to provide charge balance. While the structures shown herein do not in many cases have an explicit charge indicated, it is to be understood that the ligands and metals are selected so as to give an overall positive charge for the complex. For example, two monoanionic bidentate carbene ligands plus a third neutral XY ligand chelated to a metal with a +3 oxidation state will result in a positively charged complex. An example of this is shown below where two carbene ligands and one bypyridine ligand chelated to an Ir(III) metal give a complex with an overall charge of +1:
Figure imgf000073_0001
[0227] The carbene ligands of the cationic metal-carbene complexes are preferably multidentate. Thus, in preferred embodiments the carbene ligand has two to six bonds to the metal center, at least one of which is a carbene-metal bond. The carbene ligands discussed above, for example in tables 38-41, maybe linked by linking groups to other carbene ligands or to ancillary ligands to give tridetate, tetradentate or hexadentate ligand systems. Suitable linking groups include, for example, lower alkyl groups, ethers, alkyl-aryl-alkyl, each of which may be substituted. Additional linking groups are taught in U.S. application serial No. 10/771,423, filed February 3, 2004, which is incorporated herein by reference in its entirety. Suitable tridentate ligands are taught in co-pending application Docket No. 10020/33001, which is incorporated herein by reference in its entirety. Suitable tetradentate ligands are taught in co-pending application Docket No. 10020/33201, which is incorporated herein by reference in its entirety.
[0228] The cationic metal-carbene complexes of the present invention will generally be unsuitable for deposition using vapor deposition methods such as sublimation. Rather, the cationic metal-carbene complexes are preferably deposited using solution-based processing, such as spin coating and ink-jet printing.
[0229] Exemplary cationic carbene complexes according to the present invention are shown below:
Figure imgf000073_0002
Figure imgf000074_0001
c9 dO c11
Figure imgf000074_0002
Figure imgf000075_0001
[0230] In other embodiments, the carbene ligand may be substituted to affect charge transport. For example, a triarylamine (TAA), which has been used as a hole transport material, may be a substituent, as shown in the partial structure below:
Figure imgf000075_0002
This type of substitution may also be designed to trap charges to control recombination in the emissive layer, which may lead to more stable and efficient devices.
[0231] Other embodiments include tripodal ligands, such as those shown below.
Substituents may include groups that are believed to be emissive or have charge transport properties.
Figure imgf000075_0003
[0232] Other embodiments that may be preferred for include carbenes that exhibit improved stability or are easier to synthesize. These include hexadentate carbene complexes, which may be linked by a phenyl ring, for example:
Figure imgf000076_0001
and complexes wherein the rings of the ligand are strapped, for example:
strapped
Figure imgf000076_0002
[0233] In one embodiment, the organic layer comprises an emissive material having the formula III:
Figure imgf000076_0003
wherein:
M is a second or third row transition metal; the dotted lines represent optional double bonds;
L is an ancillary ligand;
X1 is selected from C and N;
X2 is selected from C, N, O, S and P;
X3 is selected from C and N; each Q is independently selected from a chemical bond and -C(R')2-;
Figure imgf000077_0001
Y2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N;
R1 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; a is 1 or 2; R3 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; c is 1 or 2; alternatively, R1 and R3, taken together with Y1 and Y2, form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; z s C orN;
Z2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N; R2 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; b is 1 or 2; R4 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; d is 1 or 2; 9 4 1 9 alternatively, R and R , taken together with Z and Z , form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl;
R5 and R6 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R',
C(O)OR', C(O)NR'2, aryl and heteroaryl; or alternatively, R5 and R6, taken together with X1, X2 and X3 form a 5- or 6- membered cyclic group or a 8- to 10-membered fused' bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R1 and R5 taken together with X1, Q and Y1 form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R2 and R taken together with X3, Q and Z1 form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; n is 1 or 2; and m is 0 to 3, wherein when n is 1, m is 1 to 3, and when n is 2, m is 0; wherein at least one of X2, Y2 or Z2 is C.
[0234] In preferred embodiments, M is selected from Ru, Os, Re, Rh, Ir, Pd and Pt.
In particularly preferred embodiments, M is selected from Os and Ru, and in still more preferred embodiments, M is Os. For certain preferred embodiments, Os is the preferred metal as it is relatively easy to oxidize. In further preferred embodiments, the emissive material has an oxidation potential that is more positive than about -0.7 volts, more preferably more positive than about -0.3 volts, and still more preferably more positive than about 0 volts, relative to Ferrocene/FeπOcenium cation.
[0235] In preferred embodiments of the invention, X2 of the compound according to the formula III is selected from C and N.
[0236] In another preferred embodiment, at least one of X2, Y2 or Z2 is C and is selected to be a carbene donor.
[0237] In another preferred embodiment, the compound according to the formula III is a neutral compound. Neutral compound may have the advantage of being easier to process in the manufacture of the device as they may be deposited using sublimation techniques. [0238] In the case where the compound according to the formula III is a charged compound, the compound will include a counterion to balance the charge. In this case the metal complex will have as positive charge ranging from 1+ to 6+, and preferably from 1+ to 3+. The counterion may be selected from any appropriate anion which does not interfere with the function of the compound in the device, for example, as an emissive material. The anion is selected to be electrochemically inert over the operational voltage range of the device. Preferred counteranions are typically weakly coordinating anions. The term "weakly coordinating anion" is well known in the art per se and generally refers to a large bulky anion capable of delocalization of the negative change of the anion. Suitable weakly coordinating anions, not all of which would be considered bulky, include, but are not limited to: PF6 ", BF4 ", SbCl6 ", trifluoromethansulfonate, BAr4 " (Ar = C6F5), BAr'4 " (Ar' = 3,5- bis(trifluoromethyl)phenyl, and the like. The weakly coordinating nature of such anions is known to those skilled in the art and described in the literature (S. Strauss et al., Chem. Rev., 1993, 93, 927).
[0239] In a further preferred embodiment of the invention, R5 and R are taken together with X1, X2 and X3 form a cyclic group (denoted as ring A) to give a compound having the formula IV:
Figure imgf000079_0001
wherein:
M is a second or third row transition metal; the dotted lines represent optional double bonds;
L is an ancillary ligand;
X1 is selected from C and N;
X2 is selected from C, N, O, S and P;
X3 is selected from C and N; ting A selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, wherein ring A may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') , SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each Q is independently selected from a chemical bond and -C(R')2-;
Y s C orN;
Y2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N;
R1 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; a is 1 or 2;
R3 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; c is 1 or 2; alternatively, R and R , taken together with Y and Y , form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which maybe optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; z s C orN;
Z2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N;
R2 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; b is 1 or 2;
R4 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; d is 1 or 2; alternatively, R2 and R , taken together with Z1 and Z , form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R1 and R5 taken together with X1, Q and Y1 form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R2 and R taken together with X3, Q and Z1 form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; n is 1 or 2; m is 0 to 3, wherein when n is 1, m is 1 to 3, and when n is 2, m is 0; 9 9 9 and wherein at least one of X , Y or Z is C.
[0240] In a further preferred embodiment of a compound according to the formula IV, the metal center is bound to two tridentate ligand (n=2, m=0) to give a compound having the formula V:
Figure imgf000081_0001
wherein R1, Rz, R R X1, Xz, XJ, Y1, Y , Z1, Z , M, ήngA, Q, a, b, c, and d are as described for a compound of the formula II.
[0241] Compounds which comprise two tridentate ligands are preferred. Such compounds are preferred as it is believed that such ligand configurations may improve the stability of the materials when incorporated into an organic light emitting device. Further, such materials may have the additional advantage of being more stable to sublimation during preferred deposition techniques such as OVPD.
[0242] In a further embodiment of the invention, ring A is selected to be a phenyl or pyridyl ring, which ring may be further substituted, to give a compound having the formula VI:
Figure imgf000082_0001
wherein
M is a second or third row transition metal;
X2 is selected from C or N;
R7, R8 and R9 are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2,
SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively, R5 and R6 or R6 and R7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2,
SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R1 and R7 taken together with the atoms to which they are attached form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; 9 0 additionally or alternatively R and R taken together with the atoms to which they are attached form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl;
R1, R2, R3, R4, Y1, Y2, Z1, Z2, M, Q, a, b, c, and d are as described for a compound of the formula IV.
[0243] In another embodiment of the invention, R and R are selected to form a ring
B, and R2 and R4 are selected to form a ring C to give a compound having the formula VII:
Figure imgf000083_0001
wherein: ring B and ring C are independently selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') , SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl, 1 9 1 9 1 and X , X , X , Y , Y , Z , Z , M, L, Q, a, b, c, d, n and m are as described for a compound of the formula IV.
[0244] In a further embodiment of a compound according to the formula VII, ring A is selected to be a phenyl or pyridyl ring, which ring may be further substituted, to give a compound having the formula VIII:
Figure imgf000083_0002
wherein:
X is selected from C or N; ring B and ring C are independently selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; R7, R8 and R9 are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively, R5 and R6 or R6 and R7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl. Y1, Y2, Z1, Z2, M, Q, L, n, and m are as described for a compound of the formula IV.
[0245] In a preferred embodiment of a compound according to the formula VIII, the metal center is bound to two tridentate ligand (n=2, m=0) to give a compound having the formula IX:
Figure imgf000084_0001
X is selected from C or N; ring B and ring C are independently selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; R , R and R are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively, R5 and R6 or R6 and R7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl. Y1, Y2, Z1, Z2, M and Q are as described for a compound of the formula IV.
[0246] In preferred embodiments of the invention, Q is selected to be a linking group such as -C(R')2-, rather than a chemical bond. A preferred linking group is -CH2-. For the tridentate ligands in formulas III-XII, the inclusion of a linking group may allow the metal- binding sites of the ligand to more closely achieve the preferred coordination geometry of the metal center. For example, in the preferred embodiments wherein M is Os, n = 2 and m = 0, the inclusion of linking groups for Q may allow the two tridentate ligands to more closely achieve an octahedral coordination sphere around the osmium. [0247] In a further embodiment of the invention, the emissive material has the formula X:
Figure imgf000085_0001
wherein:
M is a second or third row transition metal; X2 is selected from C or N; Q is abond or -C(R')2-;
R7, R8 and R9 are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively, R5 and R6 or R6 and R7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; 19
R is selected from alkyl, aryl and aralkyl;
R10 and R11 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2,
SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R10 and R11, or R11 and R12 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R',
C(O)OR', C(O)NR' , CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl;
R22 is selected from alkyl, aryl and aralkyl;
R20 and R21 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2,
SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively R20 and R21, or R21 and R22 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl.
[0248] In a further embodiment of the invention, the emissive material has the formula XI:
Figure imgf000086_0001
wherein
M is a second or third row transition metal;
X2 is selected from C or N;
R , R and R are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ,
SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively, R5 and R6 or R6 and R7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2,
SO , SOR', or SO3R' halo, aryl and heteroaryl; 19
R is selected from alkyl, aryl and aralkyl;
R10 and R11 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R') ,
SR', C(O)R', C(O)OR\ C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R10 and R11, or R11 and R12 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR\ C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl;
R22 is selected from alkyl, aryl and aralkyl;
R20 and R21 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2,
SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively R and R , or R and R form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R',
C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl.
[0249] In a further embodiment of the invention, the emissive material has the formula XII:
Figure imgf000087_0001
wherein: M is a second or third row transition metal; 9 9
Y and Z are independently selected from C and N;
R8, R9, R13, R14, R15, R16, R23, R24, R25, and R26 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2,
SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R8 and R9 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3,
NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R13 and R14, or R14 and R15, or R15 and R16 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively R23 and R24, or R24 and R25, or R25 and R26 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl..
[0250] Preferred substituents off of the aryl and heteroaryl groups include CF3, CN,
CH3, F, and phenyl. In preferred embodiments, the substituent R8 of compounds VI, VIII, IX, X and XI is selected from CF , CN, CH , F, and phenyl, with CF3 and CN being particularly preferred.
[0251] Preferred embodiments include osmium complexes which comprise two tridentate ligands each of which have a bond to the metal center from a carbenes and from an anionic phenyl ring, such as:
Figure imgf000088_0001
[0252] Other preferred embodiments include osmium complexes which comprise two tridentate ligands, each of which has two carbenes and one anionic phenyl ring, such as:
Figure imgf000088_0002
Figure imgf000089_0001
Figure imgf000090_0001
[0253] Other embodiments include:
Figure imgf000090_0002
[0254] In another embodiment, the emissive material is a charged compound, as exemplified below:
Figure imgf000090_0003
When the emissive material comprises a charged compound, it is understood that the material will have associated with it a counterion to balance the charge.
[0255] In certain embodiments, the organic light emitting device may comprise a material, which may be an emissive material, wherein the material comprises two tridentate ligands bound to the metal center through at least one carbon-metal bond, wherein carbon- metal bonds are not carbene-metal bonds, as exemplified below:
Figure imgf000091_0001
[0256] In some embodiments, the emissive materials are macrocyclic electrophosphors. In these embodiments, the phosphorescent emissive material comprises a heavy metal atom and a multidentate ligand system, for example a tetradentate or hexadentate ligand system. By linking two or more ligands together to give a multidentate ligand system, it is possible to increase the stability of the metal complexes formed using the ligands. [0257] In some embodiments, the donor atoms are members of a ring. The most stable complexes are formed when the internal diameter of the ring corresponds to the diameter of the cation. (Ligand Transfer Reactions - University of Fribourg, 2004, http://chimge.unil.ch/En/complexes/lcpx23.htm; See also http://www.wordiq.com/definition/Porphyrin).
[0258] In order to form a macrocyclic ligand, two or more ligands are linked to one another by a linking group. The linking group may be connected to each ligand by a covalent bond to any carbon or heteroatom of the ligand that does not interfere with the ligand's ability to bind to the metal. Linking groups include, for example, organic, organometallic, and other metal containing groups. Representative groups suitable for use as a linking group are bivalent and trivalent alkyl groups, aryl groups, silanes, ethers, and polyethers. In some embodiments, the ligands that are joined by a linking group are directly bonded to one another, in which case the term "linking group" is meant to refer to that bond. [0259] In one embodiment, two bidentate ligands are linked by a single linking group.
In another embodiment, two bidentate ligands are linked by two linking groups. The linking groups within the macrocyclic ligand can be the same or different from one another. In one embodiment, a tetradentate ligand comprises four linking groups, two of which comprise one or more linking atoms or heteroatoms and two of which are single bonds.
[0260] In one embodiment, the linking group provides no π-conjugation between the linked ligands. Having π-conjugation between the linked ligands may change the electronic properties of the ligands and the resulting metal complexes, such as a red-shift in the luminescence. It is desirable to link the ligands together to without significantly altering the electronic properties of the ligands and the resulting metal complex. A non-conjugated linking group may comprise at least one atom in the linkage, which contains no π-electrons, such as an sp3 hybridized carbon or silicon.
[0261] In one embodiment, the compound comprising the macrocyclic ligand is organometallic.
[0262] In a preferred embodiment, the ligand is symmetrical across the metal center.
Ligand symmetry may contribute to the stability of the macrocyclic ligand system.
[0263] In one embodiment, the ligand is a tetradentate ligand. When the tetradentate ligand comprises two identical bidentate ligands, the tetradentate ligand is "square."
[0264] In one embodiment, the tetradentate ligand comprises two 5-membered rings and two 6-membered rings, each ring coordinated to the metal center.
[0265] In one embodiment, the macrocyclic ligand is "planar." In the present invention, the ligand forms a plane defined by three atoms: two adjacent atoms each coordinated to the metal, and the metal atom itself. The planarity of a ligand can be determined by the angle between planes formed by the atoms coordinated to the metal, i.e., the interplanar angle. For instance, in formula XVII (described in further detail below), an interplanar angle exists between the plane of the coordinating atoms of W, X, and metal M and the plane of the coordinating atoms of Y, Z, and metal M. Likewise, an inteφlanar angle also exists between the plane of W, Z, and M and the plane of X, Y, and M.
Figure imgf000092_0001
In the planar compounds of the present invention, each interplanar angle is less than about 15°. Preferably, each interplanar angle is less than about 10°, and most preferably, each interplanar angle is about 0°.
[0266] The best way to determine if a given metal complex is a planar macrocycle system is to determine its structure by x-ray crystallography. Absent a crystal structure, a theoretical calculation can be used to predict the degree of planarity. Energy minimized structures predicted using density functional theory (DFT) closely match those determined experimentally (by x-ray methods). Other calculation methods that give similar levels of correlation between theoretical and experimental structures can also be used. See, e.g., Jason Brooks et al., "Synthesis and Characterization of Phosphorescent Cyclometallated Platinum- Complexes," Inorganic Chemistry 41(12), 3055-3066 (2002); Arnold Tamayo et al., "Synthesis and Characterization of Facial and Meridional Tris-cyclometallated Iridium (III) Complexes," Journal of the American Chemical Society 125(24), 7377-7387 (2003); Jay C. Amicangelo, "Theoretical study of a photochromic platinum complex using density functional theory methods," Abstracts of Papers, 228th ACS National Meeting, Philadelphia, PA, United States, August 22-26 (2004); Alessandro Marrone et al., "Metal Fragment Modulation of Metallacumulene Complexes: A Density Functional Study," Organometallics 23(21), 4952-4963 (2004); Irina Diaz-Acosta et al, "Calculated and experimental geometries and infrared spectra of metal tris-acetylacetonates: vibrational spectroscopy as a probe of molecular structure for ionic complexes, Part II: Spectrochimica acta, Part A: Molecular and biomolecular spectroscopy, 59(2), 363-77 (2003 Jan 15). [0267] Exemplary planar compounds include structures XV and XVI:
Figure imgf000093_0001
as well as other carbene compounds such as:
Figure imgf000093_0002
These compounds are described in further detail below.
[0268] In one embodiment, the compound of the present invention may be represented by a macrocyclic structure XIII:
Figure imgf000094_0001
wherein M is a metal; A is C orN; Zi is C orN; R1, R2, R3, and R4 are independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, heteroaryl, C(O)R', C(O)OR, or C(O)NR'2; and each of R1 and R2, R2 and R3, and R3 and R independently and optionally can form a 5- or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently R, O-R', N(R')2, SR', C(O)R', C(O)OR, C(O)NR'2, CN, CF3, NO2, SO2, SOR', SO3R', or halo, and any two J groups on adjacent ring atoms can optionally form a 5- or 6-member cyclic group; each R' is independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, or heteroaryl; Q is an ancillary ligand; n is a value from 2 to the maximum number of ligands that may be attached to metal M; m + n is the maximum number of ligands that may be attached to metal M. [0269] In some embodiments, the metal, M, is selected from the transition metals having an atomic weight greater than 40. Preferred metals for this embodiment include Ir, Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag. More preferably, the metal is Pt or Pd. Most preferably, the metal is Pt.
[0270] Many embodiments of this invention comprise substituents J. Unless otherwise specified, each substituent J is independently R', O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', SO3R, or halo, wherein any two J groups on adjacent ring atoms can optionally form a 5- or 6-member cyclic group; and wherein each R' is independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, or heteroaryl. Also, the possible cyclic groups formed by adjacent J groups may also be substituted by one or more substituents J.
[0271] Q is an optional ancillary ligand that may modify the photoactive properties of the molecule, for example by shifting the energy levels of a photoactive ligands, but it does not directly provide the energy levels involved in light emission.
[0272] In one embodiment, the present invention provides a tetradentate compound of structure XIII as described above. This embodiment is depicted as structure XV:
Figure imgf000095_0001
[0273] In this embodiment, two bidentate ligands are linked together by at least one linking group to form a tetradentate. The compounds of the present invention include structures XlVa and XI Vb:
Figure imgf000095_0002
[0274] Each of structures XlVa and XlVb form a tetradentate when the two bidentate ligands are linked to one another by at least one linking group. For example, in structure XlVa, the pair of R groups can be linked together, the pair of R4 groups can be linked together, or both pairs can be linked. Similarly, in structure XlVb, one or both of the R1 groups can be linked to its neighboring R4 group. [0275] The present invention also provides a compound having a structure XV:
Figure imgf000095_0003
wherein M is Pt or Pd; Z2 is C or Si; and the phenyl groups may be optionally substituted with one or more substituents J. [0276] In another embodiment, the present invention provides a compound having a structure XVI:
Figure imgf000096_0001
wherein M is Pt or Pd; Z2 is C or Si; and the phenyl groups may be optionally substituted with one or more substituents J. [0277] In one embodiment, the invention provides an organic light emitting device, comprising an anode, a cathode, and a phosphorescent emissive region disposed between the anode and the cathode, wherein the emissive region comprises an emissive material having the structure XVII: L1__X L2 VV M Y
XVII wherein M is a metal; W, X, Y, and Z are independently a group containing C, N, P,
O, or S coordinated to the metal M; and wherein at least one of W, X, Y, or Z is coordinated to the metal by a carbene donor. W, X, Y, and Z are linked to one another by linking groups
L1, L2, L3, and optionally L4 (x can be 0 or 1).
[0278] In a further embodiment, the emissive material has the structure XVIII:
Figure imgf000096_0002
XVIII wherein: M is a metal; the dotted lines represent optional double bonds; W1, W3, X1, X3, Y1, Y3, Z and Z3 are independently C or N; W2, X2, Y2, and Z2 are independently C, N, O, S or P; wherein at least one of W2, X2, Y2 and Z2 is a carbene; wherein for each group W, X, Y, and Z at least one of atoms 1, 2, and 3 is C; L1, L2, and L3 are independently a linking group; π R and R may optionally be joined to form a linking group L ; R1"10 are independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, heteroaryl, C(O)R', C(O)OR*, or C(O)NR'2; each of R1 and R2, R3 and R4, R5 and R6, and R9 and R10, taken together with the atoms of groups X, Y, Z, and W, respectively, can independently and optionally can form a 5- or 6-member cyclic group or an 8- to 10-membered fused bicyclic group, which may be optionally substituted by one or more substituents J; each substituent J is independently R', O-R', N(R')2, SR', C(O)R, C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', SO3R', or halo, and any two J groups on adjacent ring atoms can optionally form a 5- or 6-member cyclic group; and each R' is independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, or heteroaryl. [0279] In this embodiment, in each group W, X, Y, and Z, at least one of atoms 1, 2, and 3 is C. That is, at least one of W , W , and W is C. Similarly, at least one of X , X , and X3 is C. Groups Y and Z are likewise defined.
[0280] In a preferred embodiment of structure XVIII, R7 and R8 are joined to form a linking group L4 to give a macrocyclic compound having the structure XIX:
Figure imgf000097_0001
wherein L4 is a linking group. 1 9
[0281] In a further preferred embodiment of structure XVIII, R and R (taken together with X1, X2, and X3) form a cyclic group denoted ring A, and R3 and R4 (taken together with Y1, Y2, and Y3) form a cyclic group denoted ring B to give a compound having the structure XX:
Figure imgf000098_0001
XX wherein A and B are independently a 5- or 6-membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents J. [0282] In a further preferred embodiment of structure XX, R5 and R (taken together Q 1 fl 1 9
Z , Z , and Z ) form a cyclic group denoted ring C, and R and R (taken together W , W , and W3) form a cyclic group denoted ring D, to give a compound having the structure XXI:
Figure imgf000098_0002
XXI wherein A, B, C, and D are independently a 5- or 6-membered cyclic group or a 8- to 10- membered fused bicyclic group, which may be optionally substituted with one or more substituents J.
[0283] In a further preferred embodiment of structure XXI, R7 and R8 are joined to form a linking group L to give a compound having the structure XXII:
Figure imgf000098_0003
X wherein L4 is a linking group.
[0284] In preferred embodiments of structures XXI and XXII, all of the rings A, B, C, and D are aromatic rings. In an especially preferred embodiment, two of the rings A, B, C, and D are imidazoie rings, and each of the remaining two rings is a phenyl ring or a pyridyl ring. Accordingly, in one embodiment, the emissive material is a compound having the structure XXIII:
Figure imgf000099_0001
XXIII wherein: W τ2 and 1 Zyl are independently C or N; L2 is a linking group; R ,28 and R ,29 may optionally be joined to form a linking group L ; R ,20-32 are independently a substituent J.
[0285] In a preferred embodiment of structure XXIII, R 28 and R >29 are joined to form a linking group L to give a compound having the structure XXIV:
Figure imgf000099_0002
wherein L4 is a linking group.
[0286] In a further embodiment of the invention, the emissive material is a compound having the structure XXV:
Figure imgf000099_0003
wherein: X2 and Z are independently C or N; L1, L2, L3, and L4 are independently a linking group; R40"49 are independently a substituent J. [0287] In a preferred embodiment, the compounds according to structures XVII-
XXV are neutral compounds. Neutral compound may have the advantage of being easier to process in the manufacture of the device as they may be deposited using sublimation techniques. In the case where the compound according to structures XVII- XXV is a charged compound, the compound will include a counterion to balance the charge. The counterion maybe selected from any appropriate ion which does not interfere with the function of the compound as an emissive material.
[0288] In another embodiment of the invention, the metal-carbene complex will be cationic. Such complexes will have as positive charge ranging from 1+ to 6+, and preferably from 1+ to 2+. The cationic metal-carbene complex will be associated with a weakly coordinating anion to balance the charge. The weakly coordinating anion may be selected from any appropriate anion which does not interfere with the function of the compound in the device, for example, as an emissive material. The weakly coordinating anion is selected to be electrochemically inert over the operational voltage range of the device. The term "weakly coordinating anion" is well known in the art per se and generally refers to a large bulky anion capable of delocalization of the negative change of the anion. Suitable weakly coordinating anions, not all of which would be considered bulky, include, but are not limited to: PF6 ~, BF4 ~ SbCl6 ~ SbF<f , (Ph) B_ wherein Ph-phenyl, Ar4B" wherein Ar=C6F5, Ar'4B" wherein Ar' = 3,5-bis(trifluoromethyl)phenyl, sulfonates, and the like. The weakly coordinating nature of such anions is known to those skilled in the art and described in the literature (S. Strauss et al., Chem. Rev., 1993, 93, 927).
[0289] In some embodiments, the present invention comprises a compound further comprising one or more carbene atoms coordinated to a d8 metal. Preferred metals for this embodiment include Pt(II), Pd(II), Ir(I), Au(III), or Rh(I). Most preferably, the metal is Pt(II).
[0290] In one embodiment, the metal is coordinated to one or more carbene donors;
0-3 neutral donors; and 0-3 monoanionic donors; wherein the total number of donors is the maximum number of ligands that may be attached to the metal, and wherein each donor is optionally linked to one or more adjacent donors. In this embodiment, a donor is a group coordinated to the metal. Each donor may be optionally substituted with one or more substituents J. [0291] In one preferred embodiment, the donors are linked to form a macrocyclic ligand. In another preferred embodiment, the macrocyclic ligand is planar. In another preferred embodiment, the metal is coordinated to 4 donors, and the donors are linked to form a tetradentate ligand.
[0292] In preferred embodiments, the carbene compounds of the present invention are emissive. In one embodiment, the metal forms a carbon-metal bond with at least one carbon atom that is not a carbene donor. In a preferred embodiment, the metal forms a carbon metal bond with a phenyl group, as it is believed that this type of bonding promotes relaxation, which may result in better emissive properties. In an especially preferred embodiment, the metal is coordinated to two carbene donors and two phenyl groups. [0293] In one embodiment, the metal is coordinated to two bidentate ligands. In another embodiment, the metal is coordinated to one tridentate ligand and one monodentate ligand. In another embodiment, the metal is coordinated to a tetradentate ligand. [0294] Exemplary carbene donors include, but are not limited to:
Figure imgf000101_0001
Figure imgf000101_0002
Figure imgf000101_0003
Figure imgf000102_0001
[0295] Exemplary neutral donors include, but are not limited to
Figure imgf000102_0002
[0296] Exemplary monoanionic donors include, but are not limited to:
Figure imgf000102_0003
[0297] Preferred carbene compounds of the present invention include:
Figure imgf000102_0004
Figure imgf000103_0001
[0100] In embodiments of the invention in which the metal is selected to be a metal that preferably adopts an octahedral coordination sphere (for example, Ir, Os, Rh, Ru, etc.), the axial coordination sites may be occupied by monodentate ancillary ligands. An embodiment of such a compound is provided below:
Figure imgf000104_0001
wherein each Q is independently selected from monodentate ancillary ligands.
[0101] In some embodiments, the ligands of the present invention emit blue light, that is, the emission has CIE coordinates in the range that corresponds to saturated blue. Blue emission can be achieved by tuning the ligands. Tuning can be accomplished by altering the size of the pi system and/or adding electron donating or accepting groups. Although wavelength depends on the line width, one preferred embodiment comprises at least one ligand that has a triplet energy corresponding to a wavelength of less than 450 nm. If a small line width is achieved, for example, 40 nm or less, wavelengths longer than 450 nm would still emit the preferred saturated blue.
[0298] Like other ligand complexes used in OLEDs, planar macrocyclic ligands may show aggregation effects at moderate doping levels. This aggregation effect will lead to combined monomer and excimer/dimer emission at intermediate concentrations, and predominate excimer/dimer emission at high concentration. Monomer only emission is expected at low doping levels, but at the cost of lower efficiency. To reduce aggregation effects, sterically bulky groups may be added to the periphery of the macrocyclic ligands of the present invention. Sterically bulky groups include, but are not limited to, tertiary butyl or mesityl groups. The addition of sterically bulky groups allows for high efficiency OLEDs by allowing emission from the monomer state at high doping levels. [0299] Also provided is a process for preparing a compound having the formula
L2IrL'. The process comprises:
Figure imgf000104_0002
(a) combining and L' in the presence of an organic solvent form a mixture; (b) maintaining the mixture for sufficient time to obtain I^IrL'; (c) recovering L2IrL' from the mixture, and
where L is a carbene ligand coordinated to iridium and L' is a bidentate ligand or two monodentate ligands, and L is different from L'. L' may be a carbene or non-carbene ligand. In preferred embodiments, L and L' are both bidentate carbene ligands. In preferred embodiments, L' has a net negative charge and I^IrL' is a neutral compound. In other embodiments, L' is neutral and I^IrL' is positively charged.
[0300] Preferably, L has the structure
Figure imgf000105_0001
[0301] A may be C or N; ring B may be an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring, wherein ring B may be optionally substituted with one or more substituents R3; Ri maybe hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; R21, R22, and R3 may each independently be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, R21 and R 2, and/or two R3 groups on adjacent ring atoms may form a fused 4-7-membered aromatic group, wherein said aromatic group may be cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said aromatic group may be optionally substituted by one or more substituents J; each substituent J maybe R', CN, CF3, C(O)OR\ C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms may form a fused 4-7-membered aromatic group; each R' may be halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl. [00102] More preferably, L has the structure:
Figure imgf000105_0002
wherein R31-R34 may each be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, R21 and R22, and two R3 groups on adjacent ring atoms may form a fused 4-7- membered aromatic group, wherein said aromatic group may be cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said aromatic group may be optionally substituted by one or more substituents J; each substituent maybe R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms may form a fused 4-7-membered aromatic group; each R' may be halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl.
[0302] Most preferably, L has the structure:
Figure imgf000106_0001
[0303] Also provided are heteroleptic compounds, which may be incorporated in
OLEDs, having the structure:
Figure imgf000106_0002
These compounds may be prepared by:
(a) combining L
Figure imgf000106_0003
J * an(j in the presence of an organic solvent to form a mixture; (b) maintaining the mixture for sufficient time to obtain
Figure imgf000107_0001
(c) recovering
Figure imgf000107_0002
from the mixture.
[0304] In addition, a compound with the structure
Figure imgf000107_0003
is provided, in which L is a carbene ligand coordinated to iridium. Preferably, L has the structure:
Figure imgf000107_0004
[0305] More preferably, L has the structure:
Figure imgf000107_0005
where R31-R34 may each be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, R21 and R22j and two R3 groups on adjacent ring atoms may form a fused 4-7- membered aromatic group, wherein said aromatic group may be cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said aromatic group may be optionally substituted by one or more substituents J
[0306] Most preferably, L has the structure:
Figure imgf000108_0001
[0307] Also provided is a process for the preparing compound having the structure
Figure imgf000108_0002
The process includes the step of: (a) combining L with an organic solvent, wherein L is a suitable carbene ligand precursor; (b) maintaining the mixture of step (a) at a temperature from about 175°C to less than the boiling point of the organic solvent to obtain
(c) recovering
Figure imgf000108_0003
from the mixture. More preferably, the temperature at step (b) is at least about 185°C.
[0308] The term "suitable carbene ligand precursor," as used herein, refers to a compound which may generate a free carbene, or a reactive equivalent thereof, under the conditions used to prepare the metal carbene complexes of the present invention. It is known to those skilled in the art that a variety of precursors may be used to generate carbene ligands, including imidazolium salts, silver complexes of carbene ligands, compounds wherein RO-H or Ar-H (where Ar is pentafluorophenyl or similar aryl) are eliminated from the same carbon to generate the carbene, and olefins formally corresponding to the product of carbene-carbene dimerization.
[0309] Tris(carbene)iridium complexes have previously been synthesized by reacting a carbene ligand with an organic solvent. These reactions, which are heated to a temperature well below 175°C, are not believed to produce chlorobridged dimers in quantities sufficient to be useful as starting materials for preparing homoleptic or heteroleptic iridium carbene complexes. It has been found that when the above process is heated to temperatures greater than about 175°C (but below the temperature at which the solvent boils), the reaction becomes unexpectedly selective for chlorobridged dimer complexes. These complexes have also been found to be useful for preparing heteroleptic carbene compounds having the formula L2lrL', as previously discussed.
[0310] Also provided is a process for preparing of a compound with the formula L3Ir, wherein L is a bidentate ligand that may form a five-membered chelate ring. The process comprise:
(a) combining
Figure imgf000109_0001
and L in the presence of alcohol and a base to form a mixture; (b) maintaining the mixture for sufficient time to obtain L3Ir; and
(c) recovering L Ir from the mixture.
[0311] In preferred embodiments, L has the structure:
Figure imgf000109_0002
wherein A may be C or N; X may be an alkyl group; Y may be N, P, or C; ring B may be an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring, wherein ring B may be optionally substituted with one or more substituents R3; ring B2 may be an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M, wherein ring B2 may be optionally substituted with one or more substituents Ra ; Ri is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; R21, R22, R3) Rals Ra21, Ra22, Ra23, and Ra3 are each independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, R2ι and R22j two R3 groups, Rai and Ra21, Ra21 and Ra22, Ra22 and Ra23, and two Ra groups on adjacent ring atoms may form a fused 4-7-membered aromatic group, which may be cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said aromatic group may be optionally substituted by one or more substituents J; each substituent J maybe R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms may form a fused 4-7-membered aromatic group; each maybe halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; and b may be 0, 1, or 2. [0312] More preferably, L has the structure:
Figure imgf000110_0001
wherein R31-R 4 and Ra31-Ra34 may each be hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, R21 and R22; two R3 groups, Ra! and Ra21, Ra 1 and Ra22, Ra22 and Ra2 , and two Ra3 groups on adjacent ring atoms may form a fused 4-7-membered aromatic group, wherein said aromatic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said aromatic group may be optionally substituted by one or more substituents J; each substituent J maybe independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms may form a fused 4-7-membered aromatic group; each R' may be halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl.
[0313] Most preferably, L has the structure
Figure imgf000110_0002
[0314] In addition, compounds prepared by the above process are provided. These compounds may also be incorporated into OLEDs. Preferably these compounds have the structure:
Figure imgf000111_0001
[0315] Table 38 lists partial structures of carbene compounds ("A" part of the ligand), which in combination with the partial structures listed in Table 39 ("B" part of the ligand) make up additional embodiments. Specifically, representative embodiments include compounds having the core chemical structure of AxBy, wherein x is an integer from 1 to 47, preferably 1, 2, 5, 6, 7, 18, 19, 20, 33, or 35, and y is an integer from 1 to 86, preferably 1, 4, 10, 12, 55, 56, 59, 61, 62, 65, 66, 69, 70, 71, or 72. Preferably, the Rai substituent is an alkyl, an un-substituted aryl group, or an aryl group substituted with one or more electron donor groups, such as alkylamine, alkoxy, alkyl, or thiol groups, or electron acceptor groups, such as carboxylate, carbonyl, cyano, sulfoxide, sulfone, nitro, or phenyl groups, and the remaining Ra-substituents and Rb-substituents may be H, an alkyl group, an un-substituted aryl group, or an aryl group substituted with one or more electron donor or electron acceptor groups. Specific representative embodiments are shown in Tables 1-37, wherein the carbon and nitrogen positions are numbered for the convenient use of these tables. Some preferred embodiments are shown in Table 41. Other embodiments are shown in Table 40. [0316] Preferred "B" parts of the carbene ligand include triphenylenes, e.g., B29 and
B46, fluorenes, e.g., B55-B60, and carbazoles, e.g., B61-B66, which are believed to have high triplet energies and may be potential blue phosphors. In addition, it is well known in the art that carbazole is a stable host and is used in hole transport layers in OLEDs. Other "B" parts of the carbene ligand may be useful as red or green emitters or charge transporters. When a heteroatom not bound to the metal is present in the A or B ring, it is preferred that the heteroatom-carbon bonds are single bonds (e.g., B67, B70, B73, B76, and B79) rather than double bonds because it is believed that the heteroatom-carbon double bonds may be more susceptible to nucleophilic attacks which may lead to reduced device stability. [0317] It is also believed that nitrogen containing heterocyclic rings with no formal double bonds to the nitrogen, e.g., B67, B70, B73, B76, and B79 lead to better device stability. [0318] Each specific individual compound may be represented as "AxBy-zl -z2," wherein zl-z2 is the compound number ("Cpd No.") as shown in the tables. For the zl-z2 component, the prefix zl corresponds to the table number and the suffix z2 corresponds to the line number of that table, thus specifically identifying the individual compound. For example, for the core chemical structure of A1B1, which has two carbon atoms available for substitution on the "A" part of the ligand and four available carbon atoms on the "B" part of the ligand, Table 2 is used, since it lists specific embodiments for a structure having two available carbon atoms on the "A" part of the ligand and four available carbon atoms on the "B" part of the ligand. Thus, for the compound having the identifying number "A1B 1-2-1," Rai is methyl and Ra2, Ra3, Rbl, Rb2, Rb3 and Rb4 are each H; for "A1B1-2-2," Rai and Rbl are each methyl and Ra2, Ra3, Rb2, Rb3 and Rb4 are each H; and for "A1B1-2-3," Rai and Rb2 are each methyl and Ra2, Ra3, Rbl, Rb3 and Rb4 are each H. [0319] For AxBy complexes wherein m = 3, there are known to be two stereo- isomers, one that is typically referred to as the "mer" isomer and the other as the fac" isomer. Thus, using the compound identifying terminology, as defined herein, the mixture of both isomers is identified as "AxBy-zl-z2," whereas the "mer" isomer is identified as "mer- AxBy-zl-z2," and the "fac" isomer, as '^αc-AxBy-zl-z2." As would be understood by one skilled in the art, steric considerations may either limit or favor the synthesis of particular embodiments. For example, having large bulky groups on adjacent positions could hinder the synthesis of certain compounds. Alternatively, there may be particular groups that improve ease of synthesis, solubility, sublimation temperature, and/or thermal stability of certain compounds. For example, for each of the embodiments having a ligand with a fluorene group, such as the B55, B56 or B59 groups, or a carbazole group, such as the B61, B62, B65 or B66 groups, the methyl groups that are on the methylene carbon of fluorene groups, for example, the R7 and R8 positions on B55, or on the N-atom of the carbazole group, for example, the R7 position of B61, the methyl groups that are shown in the tables at these positions may instead readily be phenyl groups that form highly stable compounds. [0320] Thus, as specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B1, wherein M is Ir, m = 3, n = 0, and each R-substituent is H, methyl ("Me") or phenyl ("Ph."), with specific individual compounds having the core chemical structure of A1B1 being listed in Table 2. [0321] As further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A1B4, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of A1B4 being listed in Table 3.
[0322] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B10, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A1B10 being listed in Table 5.
[0323] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B12, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A1B12 being listed in Table 5.
[0324] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B55, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A1B55 being listed in Table 33
[0325] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B56, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A1B56 being listed in Table 33.
[0326] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B59, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A1B59 being listed in Table 33.
[0327] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B61, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A1B61 being listed in Table 4.
[0328] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B62, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A1B62 being listed in Table 4.
[0329] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A1B65, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of A1B65 being listed in Table 4.
[0330] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B66, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A1B66 being listed in Table 4.
[0331] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B69, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A1B69 being listed in Table 1.
[0332] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B70, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A1B70 being listed in Table 21.
[0333] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B71 , wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A1B71 being listed in Table 2.
[0334] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A1B72, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A1B72 being listed in Table 2.
[0335] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B1, wherein M is Ir, m
= 3, n = 0, with specific individual compounds having the core chemical structure of A2B1 being listed in Table 12.
[0336] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B4, wherein M is Ir, m
= 3, n = 0, with specific individual compounds having the core chemical structure of A2B4 being listed in Table 13.
[0337] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B10, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B10 being listed in Table 15. [0338] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B12, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B12 being listed in Table 15.
[0339] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B55, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B55 being listed in Table 35
[0340] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B56, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B56 being listed in Table 35.
[0341] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B59, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B59 being listed in Table 35.
[0342] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B61 , wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B61 being listed in Table 14.
[0343] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B62, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B62 being listed in Table 14.
[0344] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B65, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B65 being listed in Table 14.
[0345] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B66, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B66 being listed in Table 14.
[0346] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B69, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B69 being listed in Table 11.
[0347] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B70, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B70 being listed in Table 23.
[0348] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A2B71, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B71 being listed in Table 12.
[0349] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A2B72, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A2B72 being listed in Table 12.
[0350] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B1, wherein M is Ir, m
= 3, n = 0, with specific individual compounds having the core chemical structure of A5B1 being listed in Table 2.
[0351] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B4, wherein M is Ir, m
= 3, n = 0, with specific individual compounds having the core chemical structure of A5B4 being listed in Table 3.
[0352] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B10, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A5B 10 being listed in Table 5.
[0353] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B12, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A5B12 being listed in Table 5.
[0354] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B55, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A5B55 being listed in Table 33
[0355] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A5B56, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A5B56 being listed in Table 33.
[0356] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B59, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A5B59 being listed in Table 33.
[0357] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B61, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A5B61 being listed in Table 4.
[0358] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B62, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A5B62 being listed in Table 4.
[0359] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B65, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A5B65 being listed in Table 4.
[0360] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B66, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A5B66 being listed in Table 4.
[0361] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B69, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A5B69 being listed in Table 1.
[0362] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A5B70, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of A5B70 being listed in Table 21.
[0363] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B71, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A5B71 being listed in Table 2.
[0364] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A5B72, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A5B72 being listed in Table 2.
[0365] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B1, wherein M is Ir, m
= 3, n = 0, with specific individual compounds having the core chemical structure of A6B1 being listed in Table 17.
[0366] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B4, wherein M is Ir, m
= 3, n = 0, with specific individual compounds having the core chemical structure of A6B4 being listed in Table 18.
[0367] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B10, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B10 being listed in Table 20.
[0368] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B12, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B12 being listed in Table 20.
[0369] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B55, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B55 being listed in Table 36
[0370] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B56, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B56 being listed in Table 36. [0371] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B59, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B59 being listed in Table 36.
[0372] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B61, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B61 being listed in Table 19.
[0373] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B62, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B62 being listed in Table 19.
[0374] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A6B65, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B65 being listed in Table 19.
[0375] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B66, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B66 being listed in Table 19.
[0376] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A6B69, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B69 being listed in Table 16.
[0377] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B70, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B70 being listed in Table 24.
[0378] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B71, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B71 being listed in Table 17.
[0379] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A6B72, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A6B72 being listed in Table 17.
[0380] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A7B1, wherein M is Ir, m
= 3, n = 0, with specific individual compounds having the core chemical structure of A7B1 being listed in Table 26.
[0381] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A7B4, wherein M is Ir, m
= 3, n = 0, with specific individual compounds having the core chemical structure of A7B4 being listed in Table 28.
[0382] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A7B10, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B10 being listed in Table 30.
[0383] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A7B12, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B12 being listed in Table 30.
[0384] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A7B55, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B55 being listed in Table 37
[0385] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A7B56, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B56 being listed in Table 37.
[0386] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A7B59, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B59 being listed in Table 37.
[0387] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A7B61, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B61 being listed in Table 29.
[0388] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A7B62, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B62 being listed in Table 29.
[0389] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A7B65, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B65 being listed in Table 29.
[0390] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A7B66, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B66 being listed in Table 29.
[0391] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A7B69, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B69 being listed in Table 25.
[0392] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A7B70, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B70 being listed in Table 27.
[0393] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A7B71, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B71 being listed in Table 26.
[0394] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A7B72, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A7B72 being listed in Table 26.
[0395] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A18B1, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of A18B1 being listed in Table 12.
[0396] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of Al 8B4, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B4 being listed in Table 13.
[0397] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of Al 8B 10, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B10 being listed in Table 15.
[0398] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A18B12, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B12 being listed in Table 15.
[0399] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A18B55, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B55 being listed in Table 35
[0400] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of Al 8B56, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B56 being listed in Table 35.
[0401] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of Al 8B59, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B59 being listed in Table 35.
[0402] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A18B61, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B61 being listed in Table 14.
[0403] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of Al 8B62, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B62 being listed in Table 14. [0404] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of Al 8B65, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B65 being listed in Table 14.
[0405] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of Al 8B66, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B66 being listed in Table 14.
[0406] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A18B69, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
Al 8B69 being listed in Table 11.
[0407] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A18B70, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B70 being listed in Table 23.
[0408] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A18B71, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B71 being listed in Table 12.
[0409] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of Al 8B72, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A18B72 being listed in Table 12.
[0410] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A19B1, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B1 being listed in Table 7.
[0411] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A19B4, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B4 being listed in Table 8.
[0412] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A19B10, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B10 being listed in Table 10.
[0413] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A19B12, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B12 being listed in Table 10.
[0414] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A19B55, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B55 being listed in Table 34.
[0415] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A19B56, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B56 being listed in Table 34.
[0416] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A19B59, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B59 being listed in Table 34.
[0417] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A19B61, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B61 being listed in Table 9.
[0418] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A19B62, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B62 being listed in Table 9.
[0419] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A19B65, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B65 being listed in Table 9.
[0420] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A19B66, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B66 being listed in Table 9.
[0421] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A19B69, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B69 being listed in Table 6.
[0422] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A19B70, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B70 being listed in Table 22.
[0423] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A19B71, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B71 being listed in Table 7.
[0424] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A19B72, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A19B72 being listed in Table 7.
[0425] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B1, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B1 being listed in Table 7.
[0426] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B4, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B4 being listed in Table 8.
[0427] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B10, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B10 being listed in Table 10.
[0428] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B 12, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of A20B12 being listed in Table 10.
[0429] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B55, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B55 being listed in Table 34.
[0430] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B56, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B56 being listed in Table 34.
[0431] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B59, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B59 being listed in Table 34.
[0432] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B61, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B61 being listed in Table 9.
[0433] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B62, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B62 being listed in Table 9.
[0434] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B65, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B65 being listed in Table 9.
[0435] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B66, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B66 being listed in Table 9.
[0436] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B69, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B69 being listed in Table 6. [0437] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B70, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B70 being listed in Table 22.
[0438] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A20B71, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B71 being listed in Table 7.
[0439] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A20B72, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A20B72 being listed in Table 7.
[0440] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B1 , wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B1 being listed in Table 7.
[0441] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B4, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B4 being listed in Table 8.
[0442] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A33B 10, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B10 being listed in Table 10.
[0443] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B12, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B12 being listed in Table 10.
[0444] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B55, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B55 being listed in Table 34.
[0445] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B56, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B56 being listed in Table 34.
[0446] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B59, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B59 being listed in Table 34.
[0447] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B61, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B61 being listed in Table 9.
[0448] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B62, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B62 being listed in Table 9.
[0449] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B65, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B65 being listed in Table 9.
[0450] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B66, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B66 being listed in Table 9.
[0451] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B69, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B69 being listed in Table 6.
[0452] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B70, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B70 being listed in Table 22.
[0453] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B71, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B71 being listed in Table 7.
[0454] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A33B72, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A33B72 being listed in Table 7.
[0455] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A35B1 , wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B1 being listed in Table 17.
[0456] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A35B4, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B4 being listed in Table 18.
[0457] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A35B10, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B10 being listed in Table 20.
[0458] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A35B 12, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B12 being listed in Table 20.
[0459] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A35B55, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B55 being listed in Table 36
[0460] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A35B56, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B56 being listed in Table 36.
[0461] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A35B59, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of A35B59 being listed in Table 36.
[0462] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A35B61, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B61 being listed in Table 19.
[0463] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A35B62, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B62 being listed in Table 19.
[0464] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A35B65, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B65 being listed in Table 19.
[0465] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A35B66, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B66 being listed in Table 19.
[0466] As still further specific representative embodiments, the phosphorescent material maybe a compound having the core chemical structure of A35B69, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B69 being listed in Table 16.
[0467] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A35B70, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B70 being listed in Table 24.
[0468] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A35B71, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B71 being listed in Table 17.
[0469] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of A35B72, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of
A35B72 being listed in Table 17. [0470] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of Cl, wherein M is fr, m = 3, n = 0, with specific individual compounds having the core chemical structure of Cl being listed in Table 31.
[0471] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of C2, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of C2 being listed in Table 31.
[0472] As still further specific representative embodiments, the phosphorescent material may be a compound having the core chemical structure of C3, wherein M is Ir, m = 3, n = 0, with specific individual compounds having the core chemical structure of C3 being listed in Table 32.
[0473] Any one of the preceding specific representative embodiments may be selected so as to achieve particular desired device characteristics, for example, emission color, stability, HOMO and/or LUMO energy levels, and/or electron or hole trapping properties of the material. In addition, any one of the preceding specific representative embodiments may be further substituted, for example, with additional electron donor or electron acceptor groups, so as to further adjust certain device properties, such as emission color or stability. For example, any one of the compounds referred to in Tables 1-37 may include one or more additional methyl or phenyl groups, and/or the methyl and/or phenyl groups may be replaced with other aryl or alkyl groups such as ethyl or t-butyl. In additon, one or more of the AxBy ligands of the tr/s-iridium compound may be replaced with an ancillary "X-Y" ligand, also so as to further adjust the specific device properties, such as emission color or stability. The ancillary "X-Y" ligand may be one or more ligands selected from the group consisting of mono-dentate, bi-dentate, tri-dentate or tetra-dentate ligands. The ancillary ligand may be another organometallic ligand, such as another carbene ligand, or a non-organometallic ligand, such as acetoacetonate and others previously mentioned. Moreover, the iridium atom of any one of the preceding specific representative embodiments may be replaced with another metal atom so as to further adjust particular device properties, such as emission color or stability. The metal atom, other than Ir, may be any 3rd row transition metals, preferably Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, or Ag, more preferably, Pt, Rh, Re, Au, Os, or Ru, and most preferably, Pt. [0474] In addition, any one of the specific representative embodiments may be selected, as listed, or as further modified, so that the materials may be used as an ETL, an HTL, a hole blocking layer, an electron blocking layer, or an exciton blocking layer. In such cases, the compounds may be selected, and/or modified, so as to improve the electron and/or hole conductivity of the material.
[0475] The carbene-carbon atom that is bound to the metal atom may in some cases be conjugated with a quatemized N-alkyl unit, which in combination with the carbene-carbon atom may be drawn as a valid zwitter-ion resonance structure, with the carbene-carbon atom and the quatemized nitrogen atom being part of a heterocyclic aromatic ring, such as described in Take-aki Koizumi et al., "Terpyridine- Analogous (N,N,C)-Tridentate Ligands; Synthesis, Structures, and Electrochemical Properties of Ruthenium (II) Complexes Bearing Tridentate Pyridinium and Pyridinylidene Ligands," Organometallics, Vol 22, pp. 970-975 (2003), wherein the nitrogen atom is, for example, in the para position relative to the carbene- carbon atom. Thus, insofar as a carbene may be properly characterized as having a valid zwitter-ion resonance structure, such a ligand is represented, for example, by the ligands that include the B19 unit as part of the ligand.
[0476] One of the unifying features of the preferred representative embodiments that are specifically disclosed herein is that they all have as a core part of their chemical structure a cyclometallated, five-member, ring, which includes a metal atom bound to two carbon atoms within the ring, wherein one of the metal-carbon bonds is a metal-carbene bond and the other is a metal-mono-anionic carbon bond. Such structures are analogous to the metal-ppy- based complexes that are typically used in phosphorescent OLEDs. Such metal-ppy-based chemical structures also have a cyclometallated, five-member, ring as a core part of their chemical structure, except that the metal is bound to a single carbon atom, via a metal-mono- anionic carbon bond, and to a nitrogen atom instead of a carbene carbon. Because of the close structural analogy between the carbene-based complexes disclosed herein and metal- ppy-based complexes, it is believed herein that selection of the specifically preferred AxBy complexes may be based on considerations similar to those used to selected the preferred metal-ppy-based complexes. For example, since iridium and platinum are the most commonly preferred metals of the phosphorescent metal-ppy-based complexes, due to the very high spin-orbit coupling between the metal atom and the carbon atom, these same two metals are the most preferred metals for use in combination with the carbene-based ligands, but with iridium being more highly preferred. Similarly, it is believed that the methods and materials that have proven useful for achieving the desired characteristics for metal-ppy- based complexes, such as emission color, thermal stability, ease of chemical synthesis, solubility, sublimation temperature, HOMO and LUMO energy levels, and/or reduction of the room temperature losses in quantum efficiency due to quenching of the phosphorescence that may be observed at 77K, may also be applied to selecting the preferred metal-carbene complexes.
[0477] It is also believed that the presence of the metal-carbene bond, with its unique chemical characteristics, will lead to further particular benefits and advantages that are unique to metal-carbene complexes, and that may not be readily predicted based on their metal-ppy-based analogues.
Table 1
Cpd No. Rai Ra2 Ra3 Rbl Rb2 1- 1 Me H H H H 1- 2 Me H H Me H 1- 3 Me H H H Me 1- 4 Me H H Ph H 1- 5 Me H H H Ph 1- 6 Ph H H H H 1- 7 Ph H H Me H 1- 8 Ph H H H Me 1- 9 Ph H H Ph H 1- 10 Ph H H H Ph
1- 11 Me Me H H H 1- 12 Me Me H Me H 1- 13 Me Me H H Me 1- 14 Me Me H Ph H 1- 15 Me Me H H Ph 1- 16 Ph Me H H H 1- 17 Ph Me H Me H Cpd No. Rai Ra2 Ra3 Rbl Rb2 1-18 Ph Me H H Me 1-19 Ph Me H Ph H 1-20 Ph Me H H Ph
1-21 Me H Me H H 1-22 Me H Me Me H 1-23 Me H Me H Me 1-24 Me H Me Ph H 1-25 Me H Me H Ph 1-26 Ph H Me H H 1-27 Ph H Me Me H 1-28 Ph H Me H Me 1-29 Ph H Me Ph H 1-30 Ph H Me H Ph
1-31 Me Ph H H H 1-32 Me Ph H Me H 1-33 Me Ph H H Me 1-34 Me Ph H Ph H 1-35 Me Ph H H Ph 1-36 Ph Ph H H H 1-37 Ph Ph H Me H 1-38 Ph Ph H H Me 1-39 Ph Ph H Ph H 1-40 Ph Ph H H Ph
1-41 Me H Ph H H 1-42 Me H Ph Me H Cpd No. Rai Ra2 Ra3 Rbl Rb2 1-43 Me H Ph H Me 1-44 Me H Ph Ph H 1-45 Me H Ph H Ph 1-46 Ph H Ph H H 1-47 Ph H Ph Me H 1-48 Ph H Ph H Me 1-49 Ph H Ph Ph H 1-50 Ph H Ph H Ph
Table 2
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 2-1 Me H H H H H H 2-2 Me H H Me H H H 2-3 Me H H H Me H H 2-4 Me H H H H Me H 2-5 Me H H H H H Me 2-6 Me H H Ph H H H 2-7 Me H H H Ph H H 2-8 Me H H H H Ph H 2-9 Me H H H H H Ph 2-10 Ph H H H H H H 2-11 Ph H H Me H H H 2- 12 Ph H H H Me H H 2- 13 Ph H H H H Me H 2-14 Ph H H H H H Me 2-15 Ph H H Ph H H H 2- 16 Ph H H H Ph H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 2- 17 Ph H H H H Ph H 2- 18 Ph H H H H H Ph
2- 19 Me Me H H H H H 2-20 Me Me H Me H H H 2-21 Me Me H H Me H H 2-22 Me Me H H H Me H 2-23 Me Me H H H H Me 2-24 Me Me H Ph H H H 2-25 Me Me H H Ph H H 2-26 Me Me H H H Ph H 2-27 Me Me H H H H Ph 2-28 Ph Me H H H H H 2-29 Ph Me H Me H H H 2-30 Ph Me H H Me H H 2-31 Ph Me H H H Me H 2-32 Ph Me H H H H Me 2-33 Ph Me H Ph H H H 2-34 Ph Me H H Ph H H 2-35 Ph Me H H H Ph H 2-36 Ph Me H H H H Ph
2-37 Me H Me H H H H 2-38 Me H Me Me H H H 2-39 Me H Me H Me H H 2-40 Me H Me H H Me H 2-41 Me H Me H H H Me 2-42 Me H Me Ph H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 2-43 Me H Me H Ph H H 2-44 Me H Me H H Ph H 2-45 Me H Me H H H Ph 2-46 Ph H Me H H H H 2-47 Ph H Me Me H H H 2-48 Ph H Me H Me H H 2-49 Ph H Me H H Me H 2-50 Ph H Me H H H Me 2-51 Ph H Me Ph H H H 2-52 Ph H Me H Ph H H 2-53 Ph H Me H H Ph H 2-54 Ph H Me H H H Ph
2-55 Me Ph H H H H H 2-56 Me Ph H Me H H H 2-57 Me Ph H H Me H H 2-58 Me Ph H H H Me H 2-59 Me Ph H H H H Me 2-60 Me Ph H Ph H H H 2-61 Me Ph H H Ph H H 2-62 Me Ph H H H Ph H 2-63 Me Ph H H H H Ph 2-64 Ph Ph H H H H H 2-65 Ph Ph H Me H H H 2-66 Ph Ph H H Me H H 2-67 Ph Ph H H H Me H 2-68 Ph Ph H H H H Me 2-69 Ph Ph H Ph H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 2-70 Ph Ph H H Ph H H 2-71 Ph Ph H H H Ph H 2-72 Ph Ph H H H H Ph
2-73 Me H Ph H H H H 2-74 Me H Ph Me H H H 2-75 Me H Ph H Me H H 2-76 Me H Ph H H Me H 2-77 Me H Ph H H H Me 2-78 Me H Ph Ph H H H 2-79 Me H Ph H Ph H H 2-80 Me H Ph H H Ph H 2-81 Me H Ph H H H Ph 2-82 Ph H Ph H H H H 2-83 Ph H Ph Me H H H 2-84 Ph H Ph H Me H H 2-85 Ph H Ph H H Me H 2-86 Ph H Ph H H H Me 2-87 Ph H Ph Ph H H H 2-88 Ph H Ph H Ph H H 2-89 Ph H Ph H H Ph H 2-90 Ph H Ph H H H Ph
Table 3
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 3-1 Me H H H H H H H H 3-2 Me H H Me H H H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 3-3 Me H H H Me H H H H 3-4 Me H H H H Me H H H 3-5 Me H H H H H Me H H 3-6 Me H H H H H H Me H 3-7 Me H H H H H H H Me 3-8 Me H H Ph H H H H H 3-9 Me H H H Ph H H H H 3- 10 Me H H H H Ph H H H 3-11 Me H H H H H Ph H H 3- 12 Me H H H H H H Ph H 3-13 Me H H H H H H H Ph 3- 14 Ph H H H H H H H H 3- 15 Ph H H Me H H H H H 3- 16 Ph H H H Me H H H H 3- 17 Ph H H H H Me H H H 3-18 Ph H H H H H Me H H 3-19 Ph H H H H H H Me H 3-20 Ph H H H H H H H Me 3-21 Ph H H Ph H H H H H 3-22 Ph H H H Ph H H H H 3-23 Ph H H H H Ph H H H 3-24 Ph H H H H H Ph H H 3-25 Ph H H H H H H Ph H 3-26 Ph H H H H H H H Ph
3-27 Me Me H H H H H H H 3-28 Me Me H Me H H H H H 3-29 Me Me H H Me H H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 3-30 Me Me H H H Me H H H 3-31 Me Me H H H H Me H H 3-32 Me Me H H H H H Me H 3-33 Me Me H H H H H H Me 3-34 Me Me H Ph H H H H H 3-35 Me Me H H Ph H H H H 3-36 Me Me H H H Ph H H H 3-37 Me Me H H H H Ph H H 3-38 Me Me H H H H H Ph H 3-39 Me Me H H H H H H Ph 3-40 Ph Me H H H H H H H 3-41 Ph Me H Me H H H H H 3-42 Ph Me H H Me H H H H 3-43 Ph Me H H H Me H H H 3-44 Ph Me H H H H Me H H 3-45 Ph Me H H H H H Me H 3-46 Ph Me H H H H H H Me 3-47 Ph Me H Ph H H H H H 3-48 Ph Me H H Ph H H H H 3-49 Ph Me H H H Ph H H H 3-50 Ph Me H H H H Ph H H 3-51 Ph Me H H H H H Ph H 3-52 Ph Me H H H H H H Ph
3-53 Me H Me H H H H H H 3-54 Me H Me Me H H H H H 3-55 Me H Me H Me H H H H 3-56 Me H Me H H Me H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 3-57 Me H Me H H H Me H H 3-58 Me H Me H H H H Me H 3-59 Me H Me H H H H H Me 3-60 Me H Me Ph H H H H H 3-61 Me H Me H Ph H H H H 3-62 Me H Me H H Ph H H H 3-63 Me H Me H H" H Ph H H 3-64 Me H Me H H H H Ph H 3-65 Me H Me H H H H H Ph 3-66 Ph H Me H H H H H H 3-67 Ph H Me Me H H H H H 3-68 Ph H Me H Me H H H H 3-69 Ph H Me H H Me H H H 3-70 Ph H Me H H H Me H H 3-71 Ph H Me H H H H Me H 3-72 Ph H Me H H H H H Me 3-73 Ph H Me Ph H H H H H 3-74 Ph H Me H Ph H H H H 3-75 Ph H Me H H Ph H H H 3-76 Ph H Me H H H Ph H H 3-77 Ph H Me H H H H Ph H 3-78 Ph H Me H H H H H Ph
3-79 Me Ph H H H H H H H 3-80 Me Ph H Me H H H H H 3-81 Me Ph H H Me H H H H 3-82 Me Ph H H H Me H H H 3-83 Me Ph H H H H Me H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 3-84 Me Ph H H H H H Me H 3-85 Me Ph H H H H H H Me 3-86 Me Ph H Ph H H H H H 3-87 Me Ph H H Ph H H H H 3-88 Me Ph H H H Ph H H H 3-89 Me Ph H H H H Ph H H 3-90 Me Ph H H H H H Ph H 3-91 Me Ph H H H H H H Ph 3-92 Ph Ph H H H H H H H 3-93 Ph Ph H Me H H H H H 3-94 Ph Ph H H Me H H H H 3-95 Ph Ph H H H Me H H H 3-96 Ph Ph H H H H Me H H 3-97 Ph Ph H H H H H Me H 3-98 Ph Ph H H H H H H Me 3-99 Ph Ph H Ph H H H H H 3-100 Ph Ph H H Ph H H H H 3- 101 Ph Ph H H H Ph H H H 3- 102 Ph Ph H H H H Ph H H 3-103 Ph Ph H H H H H Ph H 3-104 Ph Ph H H H H H H Ph
3- 105 Me H Ph H H H H H H 3-106 Me H Ph Me H H H H H 3- 107 Me H Ph H Me H H H H 3-108 Me H Ph H H Me H H H 3-109 Me H Ph H H H Me H H 3-110 Me H Ph H H H H Me H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 3-111 Me H Ph H H H H H Me 3-112 Me ' H Ph Ph H H H H H 3-113 Me H Ph H Ph H H H H 3-114 Me H Ph H H Ph H H H 3-115 Me H Ph H H H Ph H H 3-116 Me H Ph H H H H Ph H 3-117 Me H Ph H H H H H Ph 3-118 Ph H Ph H H H H H H 3-119 Ph H Ph Me H H H H H 3- 120 Ph H Ph H Me H H H H 3-121 Ph H Ph H H Me H H H 3- 122 Ph H Ph H H H Me H H 3- 123 Ph H Ph H H H H Me H 3- 124 Ph H Ph H H H H H Me 3-125 Ph H Ph Ph H H H H H 3- 126 Ph H Ph H Ph H H H H 3- 127 Ph H Ph H H Ph H H H 3-128 Ph H Ph H H H Ph H H 3-129 Ph H Ph H H H H Ph H 3-130 Ph H Ph H H H H H Ph
Table 4
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 4-2 Me H H Me H H H H H Me 4-3 Me H H H Me H H H H Me 4-4 Me H H H H Me H H H Me 4-5 Me H H H H H Me H H Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 4-6 Me H H H H H H Me H Me 4-7 Me H H H H H H H Me Me 4-8 Me H H Ph H H H H H Me 4-9 Me H H H Ph H H H H Me 4- 10 Me H H H H Ph H H H Me 4- 11 Me H H H H H Ph H H Me 4-12 Me H H H H H H Ph H Me 4-13 Me H H H H H H H Ph Me 4- 14 Ph H H H H H H H H Me 4-15 Ph H H Me H H H H H Me 4- 16 Ph H H H Me H H H H Me 4- 17 Ph H H H H Me H H H Me 4- 18 Ph H H H H H Me H H Me 4- 19 Ph H H H H H H Me H Me 4-20 Ph H H H H H H H Me Me 4-21 Ph H H Ph H H H H H Me 4-22 Ph H H H Ph H H H H Me 4-23 Ph H H H H Ph H H H Me 4-24 Ph H H H H H Ph H H Me 4-25 Ph H H H H H H Ph H Me 4-26 Ph H H H H H H H Ph Me
4-27 Me Me H H H H H H H Me 4-28 Me Me H Me H H H H H Me 4-29 Me Me H H Me H H H H Me 4-30 Me Me H H H Me H H H Me 4-31 Me Me H H H H Me H H Me 4-32 Me Me H H H H H Me H Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 4-33 Me Me H H H H H H Me Me 4-34 Me Me H Ph H H H H H Me 4-35 Me Me H H Ph H H H H Me 4-36 Me Me H H H Ph H H H Me 4-37 Me Me H H H H Ph H H Me 4-38 Me Me H H H H H Ph H Me 4-39 Me Me H H H H H H Ph Me 4-40 Ph Me H H H H H H H Me 4-41 Ph Me H Me H H H H H Me 4-42 Ph Me H H Me H H H H Me 4-43 Ph Me H H H Me H H H Me 4-44 Ph Me H H H H Me H H Me 4-45 Ph Me H H H H H Me H Me 4-46 Ph Me H H H H H H Me Me 4-47 Ph Me H Ph H H H H H Me 4-48 Ph Me H H Ph H H H H Me 4-49 Ph Me H H H Ph H H H Me 4-50 Ph Me H H H H Ph H H Me 4-51 Ph Me H H H H H Ph H Me 4-52 Ph Me H H H H H H Ph Me
4-53 Me H Me H H H H H H Me 4-54 Me H Me Me H H H H H Me 4-55 Me H Me H Me H H H H Me 4-56 Me H Me H H Me H H H Me 4-57 Me H Me H H H Me H H Me 4-58 Me H Me H H H H Me H Me 4-59 Me H Me H H H H H Me Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 4-60 Me H Me Ph H H H H H Me 4-61 Me H Me H Ph H H H H Me 4-62 Me H Me H H Ph H H H Me 4-63 Me H Me H H H Ph H H Me 4-64 Me H Me H H H H Ph H Me 4-65 Me H Me H H H H H Ph Me 4-66 Ph H Me H H H H H H Me 4-67 Ph H Me Me H H H H H Me 4-68 Ph H Me H Me H H H H Me 4-69 Ph H Me H H Me H H H Me 4-70 Ph H Me H H H Me H H Me 4-71 Ph H Me H H H H Me H Me 4-72 Ph H Me H H H H H Me Me 4-73 Ph H Me Ph H H H H H Me 4-74 Ph H Me H Ph H H H H Me 4-75 Ph H Me H H Ph H H H Me 4-76 Ph H Me H H H Ph H H Me 4-77 Ph H Me H H H H Ph H Me 4-78 Ph H Me H H H H H Ph Me
4-79 Me Ph H H H H H H H Me 4-80 Me Ph H Me H H H H H Me 4-81 Me Ph H H Me H H H H Me 4-82 Me Ph H H H Me H H H Me 4-83 Me Ph H H H H Me H H Me 4-84 Me Ph H H H H H Me H Me 4-85 Me Ph H H H H H H Me Me 4-86 Me Ph H Ph H H H H H Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 4-87 Me Ph H H Ph H H H H Me 4-88 Me Ph H H H Ph H H H Me 4-89 Me Ph H H H H Ph H H Me 4-90 Me Ph H H H H H Ph H Me 4-91 Me Ph H H H H H H Ph Me 4-92 Ph Ph H H H H H H H Me 4-93 Ph Ph H Me H H H H H Me 4-94 Ph Ph H H Me H H H H Me 4-95 Ph Ph H H H Me H H H Me 4-96 Ph Ph H H H H Me H H Me 4-97 Ph Ph H H H H H Me H Me 4-98 Ph Ph H H H H H H Me Me 4-99 Ph Ph H Ph H H H H H Me 4-100 Ph Ph H H Ph H H H H Me 4-101 Ph Ph H H H Ph H H H Me 4-102 Ph Ph H H H H Ph H H Me 4-103 Ph Ph H H H H H Ph H Me 4-104 Ph Ph H H H H H H Ph Me
4-105 Me H Ph H H H H H H Me 4-106 Me H Ph Me H H H H H Me 4-107 Me H Ph H Me H H H H Me 4-108 Me H Ph H H Me H H H Me 4-109 Me H Ph H H H Me H H Me 4-110 Me H Ph H H H H Me H Me 4-111 Me H Ph H H H H H Me Me 4-112 Me H Ph Ph H H H H H Me 4-113 Me H Ph H Ph H H H H Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 4- 114 Me H Ph H H Ph H H H Me 4-115 Me H Ph H H H Ph H H Me 4-116 Me H Ph H H H H Ph H Me 4-117 Me H Ph H H H H H Ph Me 4-118 Ph H Ph H H H H H H Me 4-119 Ph H Ph Me H H H H H Me 4- 120 Ph H Ph H Me H H H H Me 4-121 Ph H Ph H H Me H H H Me 4- 122 Ph H Ph H H H Me H H Me 4-123 Ph H Ph H H H H Me H Me 4- 124 Ph H Ph H H H H H Me Me 4-125 Ph H Ph Ph H H H H H Me 4-126 Ph H Ph H Ph H H H H Me 4-127 Ph H Ph H H Ph H H H Me 4-128 Ph H Ph H H H Ph H H Me 4-129 Ph H Ph H H H H Ph H Me 4-130 Ph H Ph H H H H H Ph Me
Table 5
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 5-1 Me H H H H H H H H H H 5-2 Me H H Me H H H H H H H 5-3 Me H H H Me H H H H H H 5-4 Me H H H H Me H H H H H 5-5 Me H H H H H Me H H H H 5-6 Me H H H H H H Me H H H 5-7 Me H H H H H H H Me H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 5-8 Me H H H H H H H H Me H 5-9 Me H H H H H H H H H Me 5-10 Me H H Ph H H H H H H H 5-11 Me H H H Ph H H H H H H 5-12 Me H H H H Ph H H H H H 5-13 Me H H H H H Ph H H H H 5-14 Me H H H H H H Ph H H H 5-15 Me H H H H H H H Ph H H 5-16 Me H H H H H H H H Ph H 5-17 Me H H H H H H H H H Ph 5-18 Ph H H H H H H H H H H 5-19 Ph H H Me H H H H H H H 5-20 Ph H H H Me H H H H H H 5-21 Ph H H H H Me H H H H H 5-22 Ph H H H H H Me H H H H 5-23 Ph H H H H H H Me H H H 5-24 Ph H H H H H H H Me H H 5-25 Ph H H H H H H H H Me H 5-26 Ph H H H H H H H H H Me 5-27 Ph H H Ph H H H H H H H 5-28 Ph H H H Ph H H H H H H 5-29 Ph H H H H Ph H H H H H 5-30 Ph H H H H H Ph H H H H 5-31 Ph H H H H H H Ph H H H 5-32 Ph H H H H H H H Ph H H 5-33 Ph H H H H H H H H Ph H 5-34 Ph H H H H H H H H H Ph Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 5-35 Me Me H H H H H H H H H 5-36 Me Me H Me H H H H H H H 5-37 Me Me H H Me H H H H H H 5-38 Me Me H H H Me H H H H H 5-39 Me Me H H H H Me H H H H 5-40 Me Me H H H H H Me H H H 5-41 Me Me H H H H H H Me H H 5-42 Me Me H H H H H H H Me H 5-43 Me Me H H H H H H H H Me 5-44 Me Me H Ph H H H H H H H 5-45 Me Me H H Ph H H H H H H 5-46 Me Me H H H Ph H H H H H 5-47 Me Me H H H H Ph H H H H 5-48 Me Me H H H H H Ph H H H 5-49 Me Me H H H H H H Ph H H 5-50 Me Me H H H H H H H Ph H 5-51 Me Me H H H H H H H H Ph 5-52 Ph Me H H H H H H H H H 5-53 Ph Me H Me H H H H H H H 5-54 Ph Me H H Me H H H H H H 5-55 Ph Me H H H Me H H H H H 5-56 Ph Me H H H H Me H H H H 5-57 Ph Me H H H H H Me H H H 5-58 Ph Me H H H H H H Me H H 5-59 Ph Me H H H H H H H Me H 5-60 Ph Me H H H H H H H H Me 5-61 Ph Me H Ph H H H H H H H 5-62 Ph Me H H Ph H H H H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 5-63 Ph Me H H H Ph H H H H H 5-64 Ph Me H H H H Ph H H H H 5-65 Ph Me H H H H H Ph H H H 5-66 Ph Me H H H H H H Ph H H 5-67 Ph Me H H H H H H H Ph H 5-68 Ph Me H H H H H H H H Ph
5-69 Me H Me H H H H H H H H 5-70 Me H Me Me H H H H H H H 5-71 Me H Me H Me H H H H H H 5-72 Me H Me H H Me H H H H H 5-73 Me H Me H H H Me H H H H 5-74 Me H Me H H H H Me H H H 5-75 Me H Me H H H H H Me H H 5-76 Me H Me H H H H H H Me H 5-77 Me H Me H H H H H H H Me 5-78 Me H Me Ph H H H H H H H 5-79 Me H Me H Ph H H H H H H 5-80 Me H Me H H Ph H H H H H 5-81 Me H Me H H H Ph H H H H 5-82 Me H Me H H H H Ph H H H 5-83 Me H Me H H H H H Ph H H 5-84 Me H Me H H H H H H Ph H 5-85 Me H Me H H H H H H H Ph 5-86 Ph H Me H H H H H H H H 5-87 Ph H Me Me H H H H H H H 5-88 Ph H Me H Me H H H H H H 5-89 Ph H Me H H Me H H H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 5-90 Ph H Me H H H Me H H H H 5-91 Ph H Me H H H H Me H H H 5-92 Ph H Me H H H H H Me H H 5-93 Ph H Me H H H H H H Me H 5-94 Ph H Me H H H H H H H Me 5-95 Ph H Me Ph H H H H H H H 5-96 Ph H Me H Ph H H H H H H 5-97 Ph H Me H H Ph H H H H H 5-98 Ph H Me H H H Ph H H H H 5-99 Ph H Me H H H H Ph H H H 5- 100 Ph H Me H H H H H Ph H H 5- 101 Ph H Me H H H H H H Ph H 5-102 Ph H Me H H H H H H H Ph
5- 103 Me Ph H H H H H H H H H 5- 104 Me Ph H Me H H H H H H H 5- 105 Me Ph H H Me H H H H H H 5-106 Me Ph H H H Me H H H H H 5-107 Me Ph H H H H Me H H H H 5-108 Me Ph H H H H H Me H H H 5-109 Me Ph H H H H H H Me H H 5-110 Me Ph H H H H H H H Me H 5-111 Me Ph H H H H H H H H Me 5- 112 Me Ph H Ph H H H H H H H 5-113 Me Ph H H Ph H H H H H H 5-114 Me Ph H H H Ph H H H H H 5-115 Me Ph H H H H Ph H H H H 5-116 Me Ph H H H H H Ph H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 5-117 Me Ph H H H H H H Ph H H 5-118 Me Ph H H H H H H H Ph H 5-119 Me Ph H H H H H H H H Ph 5- 120 Ph Ph H H H H H H H H H 5-121 Ph Ph H Me H H H H H H H 5- 122 Ph Ph H H Me H H H H H H 5- 123 Ph Ph H H H Me H H H H H 5-124 Ph Ph H H H H Me H H H H 5- 125 Ph Ph H H H H H Me H H H 5-126 Ph Ph H H H H H H Me H H 5-127 Ph Ph H H H H H H H Me H 5-128 Ph Ph H H H H H H H H Me 5-129 Ph Ph H Ph H H H H H H H 5- 130 Ph Ph H H Ph H H H H H H 5-131 Ph Ph H H H Ph H H H H H 5-132 Ph Ph H H H H Ph H H H H 5-133 Ph Ph H H H H H Ph H H H 5-134 Ph Ph H H H H H H Ph H H 5-135 Ph Ph H H H H H H H Ph H 5-136 Ph Ph H H H H H H H H Ph
5-137 Me H Ph H H H H H H H H 5-138 Me H Ph Me H H H H H H H 5-139 Me H Ph H Me H H H H H H 5- 140 Me H Ph H H Me H H H H H 5-141 Me H Ph H H H Me H H H H 5-142 Me H Ph H H H H Me H H H 5-143 Me H Ph H H H H H Me H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 5-144 Me H Ph H H H H H H Me H 5-145 Me H Ph H H H H H H H Me 5-146 Me H Ph Ph H H H H H H H 5-147 Me H Ph H Ph H H H H H H 5-148 Me H Ph H H Ph H H H H H 5-149 Me H Ph H H H Ph H H H H 5- 150 Me H Ph H H H H Ph H H H 5- 151 Me H Ph H H H H H Ph H H 5-152 Me H Ph H H H H H H Ph H 5-153 Me H Ph H H H H H H H Ph 5-154 Ph H Ph H H H H H H H H 5- 155 Ph H Ph Me H H H H H H H 5-156 Ph H Ph H Me H H H H H H 5-157 Ph H Ph H H Me H H H H H 5- 158 Ph H Ph H H H Me H H H H 5-159 Ph H Ph H H H H Me H H H 5-160 Ph H Ph H H H H H Me H H 5-161 Ph H Ph H H H H H H Me H 5-162 Ph H Ph H H H H H H H Me 5-163 Ph H Ph Ph H H H H H H H 5-164 Ph H Ph H Ph H H H H H H 5- 165 Ph H Ph H H Ph H H H H H 5-166 Ph H Ph H H H Ph H H H H 5- 167 Ph H Ph H H H H Ph H H H 5-168 Ph H Ph H H H H H Ph H H 5-169 Ph H Ph H H H H H H Ph H 5-170 Ph H Ph H H H H H H H Ph Table 6
Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2
6-1 Me H H H H H 6-2 Me H H H Me H 6-3 Me H H H H Me 6-4 Me H H H Ph H 6-5 Me H H H H Ph 6-6 Ph H H H H H 6-7 Ph H H H Me H 6-8 Ph H H H H Me 6-9 Ph H H H Ph H 6- 10 Ph H H H H Ph
6- 11 Me Me H H H H 6- 12 Me Me H H Me H 6- 13 Me Me H H H Me 6-14 Me Me H H Ph H 6-15 Me Me H H H Ph 6- 16 Ph Me H H H H 6- 17 Ph Me H H Me H 6-18 Ph Me H H H Me 6-19 Ph Me H H Ph H 6-20 Ph Me H H H Ph
6-21 Me H Me H H H 6-22 Me H Me H Me H 6-23 Me H Me H H Me 6-24 Me H Me H Ph H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 6-25 Me H Me H H Ph 6-26 Ph H Me H H H 6-27 Ph H Me H Me H 6-28 Ph H Me H H Me 6-29 Ph H Me H Ph H 6-30 Ph H Me H H Ph
6-31 Me H H Me H H 6-32 Me H H Me Me H 6-33 Me H H Me H Me 6-34 Me H H Me Ph H 6-35 Me H H Me H Ph 6-36 Ph H H Me H H 6-37 Ph H H Me Me H 6-38 Ph H H Me H Me 6-39 Ph H H Me Ph H 6-40 Ph H H Me H Ph
6-41 Me Ph H H H H 6-42 Me Ph H H Me H 6-43 Me Ph H H H Me 6-44 Me Ph H H Ph H 6-45 Me Ph H H H Ph 6-46 Ph Ph H H H H 6-47 Ph Ph H H Me H 6-48 Ph Ph H H H Me 6-49 Ph Ph H H Ph H 6-50 Ph Ph H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 6-51 Me H Ph H H H 6-52 Me H Ph H Me H 6-53 Me H Ph H H Me 6-54 Me H Ph H Ph H 6-55 Me H Ph H H Ph 6-56 Ph H Ph H H H 6-57 Ph H Ph H Me H 6-58 Ph H Ph H H Me 6-59 Ph H Ph H Ph H 6-60 Ph H Ph H H Ph
6-61 Me H H Ph H H 6-62 Me H H Ph Me H 6-63 Me H H Ph H Me 6-64 Me H H Ph Ph H 6-65 Me H H Ph H Ph 6-66 Ph H H Ph H H 6-67 Ph H H Ph Me H 6-68 Ph H H Ph H Me 6-69 Ph H H Ph Ph H 6-70 Ph H H Ph H Ph
Table 7
Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 7- 1 Me H H H H H H H 7-2 Me H H H Me H H H 7-3 Me H H H H Me H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 7-4 Me H H H H H Me H 7-5 Me H H H H H H Me 7-6 Me H H H Ph H H H 7-7 Me H H H H Ph H H 7-8 Me H H H H H Ph H 7-9 Me H H H H H H Ph 7-10 Ph H H H H H H H 7-11 Ph H H H Me H H H 7-12 Ph H H H H Me H H 7-13 Ph H H H H H Me H 7-14 Ph H H H H H H Me 7-15 Ph H H H Ph H H H 7-16 Ph H H H H Ph H H 7-17 Ph H H H H H Ph H 7-18 Ph H H H H H H Ph
7- 19 Me Me H H H H H H 7-20 Me Me H H Me H H H 7-21 Me Me H H H Me H H 7-22 Me Me H H H H Me H 7-23 Me Me H H H H H Me 7-24 Me Me H H Ph H H H 7-25 Me Me H H H Ph H H 7-26 Me Me H H H H Ph H 7-27 Me Me H H H H H Ph 7-28 Ph Me H H H H H H 7-29 Ph Me H H Me H H H 7-30 Ph Me H H H Me H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 7-31 Ph Me H H H H Me H 7-32 Ph Me H H H H H Me 7-33 Ph Me H H Ph H H H 7-34 Ph Me H H H Ph H H 7-35 Ph Me H H H H Ph H 7-36 Ph Me H H H H H Ph
7-37 Me H Me H 7-38 Me H Me H Me H H H 7-39 Me H Me H H Me H H 7-40 Me H Me H H H Me H 7-41 Me H Me H H H H Me 7-42 Me H Me H Ph H H H 7-43 Me H Me H H Ph H H 7-44 Me H Me H H H Ph H 7-45 Me H Me H H H H Ph 7-46 Ph H Me H H H H H 7-47 Ph H Me H Me H H H 7-48 Ph H Me H H Me H H 7-49 Ph H Me H H H Me H 7-50 Ph H Me H H H H Me 7-51 Ph H Me H Ph H H H 7-52 Ph H Me H H Ph H H 7-53 Ph H Me H H H Ph H 7-54 Ph H Me H H H H Ph
7-55 Me H H Me 7-56 Me H H Me Me H H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 7-57 Me H H Me H Me H H 7-58 Me H H Me H H Me H 7-59 Me H H Me H H H Me 7-60 Me H H Me Ph H H H 7-61 Me H H Me H Ph H H 7-62 Me H H Me H H Ph H 7-63 Me H H Me H H H Ph 7-64 Ph H H Me H H H H 7-65 Ph H H Me Me H H H 7-66 Ph H H Me H Me H H 7-67 Ph H H Me H H Me H 7-68 Ph H H Me H H H Me 7-69 Ph H H Me Ph H H H 7-70 Ph H H Me H Ph H H 7-71 Ph H H Me H H Ph H 7-72 Ph H H Me H H H Ph
7-73 Me Ph H H H H H H 7-74 Me Ph H H Me H H H 7-75 Me Ph H H H Me H H 7-76 Me Ph H H H H Me H 7-77 Me Ph H H H H H Me 7-78 Me Ph H H Ph H H H 7-79 Me Ph H H H Ph H H 7-80 Me Ph H H H H Ph H 7-81 Me Ph H H H H H Ph 7-82 Ph Ph H H H H H H 7-83 Ph Ph H H Me H H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 7-84 Ph Ph H H H Me H H 7-85 Ph Ph H H H H Me H 7-86 Ph Ph H H H H H Me 7-87 Ph Ph H H Ph H H H 7-88 Ph Ph H H H Ph H H 7-89 Ph Ph H H H H Ph H 7-90 Ph Ph H H H H H Ph
7-91 Me H Ph H H H H H 7-92 Me H Ph H Me H H H 7-93 Me H Ph H H Me H H 7-94 Me H Ph H H H Me H 7-95 Me H Ph H H H H Me 7-96 Me H Ph H Ph H H H 7-97 Me H Ph H H Ph H H 7-98 Me H Ph H H H Ph H 7-99 Me H Ph H H H H Ph 7- 100 Ph H Ph H H H H H 7- 101 Ph H Ph H Me H H H 7- 102 Ph H Ph H H Me H H 7- 103 Ph H Ph H H H Me H 7- 104 Ph H Ph H H H H Me 7- 105 Ph H Ph H Ph H H H 7-106 Ph H Ph H H Ph H H 7-107 Ph H Ph H H H Ph H 7- 108 Ph H Ph H H H H Ph
7-109 Me H H Ph H H H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 7-110 Me H H Ph Me H H H 7-111 Me H H Ph H Me H H 7-112 Me H H Ph H H Me H 7- 113 Me H H Ph H H H Me 7-114 Me H H Ph Ph H H H 7-115 Me H H Ph H Ph H H 7-116 Me H H Ph H H Ph H 7-117 Me H H Ph H H H Ph 7- 118 Ph H H Ph H H H H 7- 119 Ph H H Ph Me H H H 7- 120 Ph H H Ph H Me H H 7- 121 Ph H H Ph H H Me H 7-122 Ph H H Ph H H H Me 7-123 Ph H H Ph Ph H H H 7-124 Ph H H Ph H Ph H H 7- 125 Ph H H Ph H H Ph H 7- 126 Ph H H Ph H H H Ph
Table 8
Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 8-1 Me H H H H H H H H H 8-2 Me H H H Me H H H H H 8-3 Me H H H H Me H H H H 8-4 Me H H H H H Me H H H 8-5 Me H H H H H H Me H H 8-6 Me H H H H H H H Me H 8-7 Me H H H H H H H H Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 8-8 Me H H H Ph H H H H H 8-9 Me H H H H Ph H H H H 8-10 Me H H H H H Ph H H H 8-11 Me H H H H H H Ph H H 8-12 Me H H H H H H H Ph H 8- 13 Me H H H H H H H H Ph 8-14 Ph H H H H H H H H H 8- 15 Ph H H H Me H H H H H 8-16 Ph H H H H Me H H H H 8-17 Ph H H H H H Me H H H 8-18 Ph H H H H H H Me H H 8-19 Ph H H H H H H H Me H 8-20 Ph H H H H H H H H Me 8-21 Ph H H H Ph H H H H H 8-22 Ph H H H H Ph H H H H 8-23 Ph H H H H H Ph H H H 8-24 Ph H H H H H H Ph H H 8-25 Ph H H H H H H H Ph H 8-26 Ph H H H H H H H H Ph
8-27 Me Me H H H H H H H H 8-28 Me Me H H Me H H H H H 8-29 Me Me H H H Me H H H H 8-30 Me Me H H H H Me H H H 8-31 Me Me H H H H H Me H H 8-32 Me Me H H H H H H Me H 8-33 Me Me H H H H H H H Me 8-34 Me Me H H Ph H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 8-35 Me Me H H H Ph H H H H 8-36 Me Me H H H H Ph H H H 8-37 Me Me H H H H H Ph H H 8-38 Me Me H H H H H H Ph H 8-39 Me Me H H H H H H H Ph 8-40 Ph Me H H H H H H H H 8-41 Ph Me H H Me H H H H H 8-42 Ph Me H H H Me H H H H 8-43 Ph Me H H H H Me H H H 8-44 Ph Me H H H H H Me H H 8-45 Ph Me H H H H H H Me H 8-46 Ph Me H H H H H H H Me 8-47 Ph Me H H Ph H H H H H 8-48 Ph Me H H H Ph H H H H
. 8-49 Ph Me H H H H Ph H H H 8-50 Ph Me H H H H H Ph H H 8-51 Ph Me H H H H H H Ph H 8-52 Ph Me H H H H H H H Ph
8-53 Me H Me H H H H H H H 8-54 Me H Me H Me H H H H H 8-55 Me H Me H H Me H H H H 8-56 Me H Me H H H Me H H H 8-57 Me H Me H H H H Me H H 8-58 Me H Me H H H H H Me H 8-59 Me H Me H H H H H H Me 8-60 Me H Me H Ph H H H H H 8-61 Me H Me H H Ph H H H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 8-62 Me H Me H H H Ph H H H 8-63 Me H Me H H H H Ph H H 8-64 Me H Me H H H H H Ph H 8-65 Me H Me H H H H H H Ph 8-66 Ph H Me H H H H H H H 8-67 Ph H Me H Me H H H H H 8-68 Ph H Me H H Me H H H H 8-69 Ph H Me H H H Me H H H 8-70 Ph H Me H H H H Me H H 8-71 Ph H Me H H H H H Me H 8-72 Ph H Me H H H H H H Me 8-73 Ph H Me H Ph H H H H H 8-74 Ph H Me H H Ph H H H H 8-75 Ph H Me H H H Ph H H H 8-76 Ph H Me H H H H Ph H H 8-77 Ph H Me H H H H H Ph H 8-78 Ph H Me H H H H H H Ph
8-79 Me H H Me H H H H H H 8-80 Me H H Me Me H H H H H 8-81 Me H H Me H Me H H H H 8-82 Me H H Me H H Me H H H 8-83 Me H H Me H H H Me H H 8-84 Me H H Me H H H H Me H 8-85 Me H H Me H H H H H Me 8-86 Me H H Me Ph H H H H H 8-87 Me H H Me H Ph H H H H 8-88 Me H H Me H H Ph H H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 8-89 Me H H Me H H H Ph H H 8-90 Me H H Me H H H H Ph H 8-91 Me H H Me H H H H H Ph 8-92 Ph H H Me H H H H H H 8-93 Ph H H Me Me H H H H H 8-94 Ph H H Me H Me H H H H 8-95 Ph H H Me H H Me H H H 8-96 Ph H H Me H H H Me H H 8-97 Ph H H Me H H H H Me H 8-98 Ph H H Me H H H H H Me 8-99 Ph H H Me Ph H H H H H 8-100 Ph H H Me H Ph H H H H 8-101 Ph H H Me H H Ph H H H 8-102 Ph H H Me H H H Ph H H 8-103 Ph H H Me H H H H Ph H 8-104 Ph H H Me H H H H H Ph
8-105 Me Ph H H H H H H H H 8-106 Me Ph H H Me H H H H H 8-107 Me Ph H H H Me H H H H 8-108 Me Ph H H H H Me H H H 8-109 Me Ph H H H H H Me H H 8-110 Me Ph H H H H H H Me H 8-111 Me Ph H H H H H H H Me 8-112 Me Ph H H Ph H H H H H 8-113 Me Ph H H H Ph H H H H 8-114 Me Ph H H H H Ph H H H 8-115 Me Ph H H H H H Ph H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 8- 116 Me Ph H H H H H H Ph H 8-117 Me Ph H H H H H H H Ph 8-118 Ph Ph H H H H H H H H 8-119 Ph Ph H H Me H H H H H 8-120 Ph Ph H H H Me H H H H 8- 121 Ph Ph H H H H Me H H H 8- 122 Ph Ph H H H H H Me H H 8- 123 Ph Ph H H H H H H Me H 8- 124 Ph Ph H H H H H H H Me 8-125 Ph Ph H H Ph H H H H H 8- 126 Ph Ph H H H Ph H H H H 8-127 Ph Ph H H H H Ph H H H 8- 128 Ph Ph H H H H H Ph H H 8- 129 Ph Ph H H H H H H Ph H 8- 130 Ph Ph H H H H H H H Ph
8- 131 Me H Ph H H H H H H H 8- 132 Me H Ph H Me H H H H H 8- 133 Me H Ph H H Me H H H H 8-134 Me H Ph H H H Me H H H 8-135 Me H Ph H H H H Me H H 8- 136 Me H Ph H H H H H Me H 8-137 Me H Ph H H H H H H Me 8-138 Me H Ph H Ph H H H H H 8-139 Me H Ph H H Ph H H H H 8-140 Me H Ph H H H Ph H H H 8- 141 Me H Ph H H H H Ph H H 8-142 Me H Ph H H H H H Ph H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 8-143 Me H Ph H H H H H H Ph 8- 144 Ph H Ph H H H H H H H 8-145 Ph H Ph H Me H H H H H 8-146 Ph H Ph H H Me H H H H 8-147 Ph H Ph H H H Me H H H 8-148 Ph H Ph H H H H Me H H 8-149 Ph H Ph H H H H H Me H 8- 150 Ph H Ph H H H H H H Me 8-151 Ph H Ph H Ph H H H H H 8- 152 Ph H Ph H H Ph H H H H 8- 153 Ph H Ph H H H Ph H H H 8- 154 Ph H Ph H H H H Ph H H 8- 155 Ph H Ph H H H H H Ph H 8- 156 Ph H Ph H H H H H H Ph
8- 157 Me H H Ph H H H H H H 8- 158 Me H H Ph Me H H H H H 8-159 Me H H Ph H Me H H H H 8- 160 Me H H Ph H H Me H H H 8- 161 Me H H Ph H H H Me H H 8- 162 Me H H Ph H H H H Me H 8- 163 Me H H Ph H H H H H Me 8-164 Me H H Ph Ph H H H H H 8- 165 Me H H Ph H Ph H H H H 8-166 Me H H Ph H H Ph H H H 8-167 Me H H Ph H H H Ph H H 8-168 Me H H Ph H H H H Ph H 8-169 Me H H Ph H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 8- 170 Ph H H Ph H H H H H H 8-171 Ph H H Ph Me H H H H H 8- 172 Ph H H Ph H Me H H H H 8-173 Ph H H Ph H H Me H H H 8-174 Ph H H Ph H H H Me H H 8-175 Ph H H Ph H H H H Me H 8- 176 Ph H H Ph H H H H H Me 8-177 Ph H H Ph Ph H H H H H 8-178 Ph H H Ph H Ph H H H H 8-179 Ph H H Ph H H Ph H H H 8-180 Ph H H Ph H H H Ph H H 8-181 Ph H H Ph H H H H Ph H 8-182 Ph H H Ph H H H H H Ph
Table 9
Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9-1 Me H H H H H H H H H Me 9-2 Me H H H Me H H H H H Me 9-3 Me H H H H Me H H H H Me 9-4 Me H H H H H Me H H H Me 9-5 Me H H H H H H Me H H Me 9-6 Me H H H H H H H Me H Me 9-7 Me H H H H H H H H Me Me 9-8 Me H H H Ph H H H H H Me 9-9 Me H H H H Ph H H H H Me 9-10 Me H H H H H Ph H H H Me 9-11 Me H H H H H H Ph H H Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9- 12 Me H H H H H H H Ph H Me 9-13 Me H H H H H H H H Ph Me 9-14 Ph H H H H H H H H H Me 9-15 Ph H H H Me H H H H H Me 9- 16 Ph H H H H Me H H H H Me 9-17 Ph H H H H H Me H H H Me 9-18 Ph H H H H H H Me H H Me 9-19 Ph H H H H H H H Me H Me 9-20 Ph H H H H H H H H Me Me 9-21 Ph H H H Ph H H H H H Me 9-22 Ph H H H H Ph H H H H Me 9-23 Ph H H H H H Ph H H H Me 9-24 Ph H H H H H H Ph H H Me 9-25 Ph H H H H H H H Ph H Me 9-26 Ph H H H H H H H H Ph Me
9-27 Me Me H H H H H H H H Me 9-28 Me Me H H Me H H H H H Me 9-29 Me Me H H H Me H H H H Me 9-30 Me Me H H H H Me H H H Me 9-31 Me Me H H H H H Me H H Me 9-32 Me Me H H H H H H Me H Me 9-33 Me Me H H H H H H H Me Me 9-34 Me Me H H Ph H H H H H Me 9-35 Me Me H H H Ph H H H H Me 9-36 Me Me H H H H Ph H H H Me 9-37 Me Me H H H H H Ph H H Me 9-38 Me Me H H H H H H Ph H Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9-39 Me Me H H H H H H H Ph Me 9-40 Ph Me H H H H H H H H Me 9-41 Ph Me H H Me H H H H H Me 9-42 Ph Me H H H Me H H H H Me 9-43 Ph Me H H H H Me H H H Me 9-44 Ph Me H H H H H Me H H Me 9-45 Ph ' Me H H H H H H Me H Me 9-46 Ph Me H H H H H H H Me Me 9-47 Ph Me H H Ph H H H H H Me 9-48 Ph Me H H H Ph H H H H Me 9-49 Ph Me H H H H Ph H H H Me 9-50 Ph Me H H H H H Ph H H Me 9-51 Ph Me H H H H H H Ph H Me 9-52 Ph Me H H H H H H H Ph Me
9-53 Me H Me H H H H H H H Me 9-54 Me H Me H Me H H H H H Me 9-55 Me H Me H H Me H H H H Me 9-56 Me H Me H H H Me H H H Me 9-57 Me H Me H H H H Me H H Me 9-58 Me H Me H H H H H Me H Me 9-59 Me H Me H H H H H H Me Me 9-60 Me H Me H Ph H H H H H Me 9-61 Me H Me H H Ph H H H H Me 9-62 Me H Me H H H Ph H H H Me 9-63 Me H Me H H H H Ph H H Me 9-64 Me H Me H H H H H Ph H Me 9-65 Me H Me H H H H H H Ph Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9-66 Ph H Me H H H H H H H Me 9-67 Ph H Me H Me H H H H H Me 9-68 Ph H Me H H Me H H H H Me 9-69 Ph H Me H H H Me H H H Me 9-70 Ph H Me H H H H Me H H Me 9-71 Ph H Me H H H H H Me H Me 9-72 Ph H Me H H H H H H Me Me 9-73 Ph H Me H Ph H H H H H Me 9-74 Ph H Me H H Ph H H H H Me 9-75 Ph H Me H H H Ph H H H Me 9-76 Ph H Me H H H H Ph H H Me 9-77 Ph H Me H H H H H Ph H Me 9-78 Ph H Me H H H H H H Ph Me
9-79 Me H H Me H H H H H H Me 9-80 Me H H Me Me H H H H H Me 9-81 Me H H Me H Me H H H H Me 9-82 Me H H Me H H Me H H H Me 9-83 Me H H Me H H H Me H H Me 9-84 Me H H Me H H H H Me H Me 9-85 Me H H Me H H H H H Me Me 9-86 Me H H Me Ph H H H H H Me 9-87 Me H H Me H Ph H H H H Me 9-88 Me H H Me H H Ph H H H Me 9-89 Me H H Me H H H Ph H H Me 9-90 Me H H Me H H H H Ph H Me 9-91 Me H H Me H H H H H Ph Me 9-92 Ph H H Me H H H H H H Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9-93 Ph H H Me Me H H H H H Me 9-94 Ph H H Me H Me H H H H Me 9-95 Ph H H Me H H Me H H H Me 9-96 Ph H H Me H H H Me H H Me 9-97 Ph H H Me H H H H Me H Me 9-98 Ph H H Me H H H H H Me Me 9-99 Ph H H Me Ph H H H H H Me 9- 100 Ph H H Me H Ph H H H H Me 9- 101 Ph H H Me H H Ph H H H Me 9- 102 Ph H H Me H H H Ph H H Me 9-103 Ph H H Me H H H H Ph H Me 9-104 Ph H H Me H H H H H Ph Me
9- 105 Me Ph H H H H H H H H Me 9-106 Me Ph H H Me H H H H H Me 9-107 Me Ph H H H Me H H H H Me 9- 108 Me Ph H H H H Me H H H Me 9- 109 Me Ph H H H H H Me H H Me 9- 110 Me Ph H H H H H H Me H Me 9- 111 Me Ph H H H H H H H Me Me 9- 112 Me Ph H H Ph H H H H H Me 9- 113 Me Ph H H H Ph H H H H Me 9-114 Me Ph H H H H Ph H H H Me 9- 115 Me Ph H H H H H Ph H H Me 9-116 Me Ph H H H H H H Ph H Me 9-117 Me Ph H H H H H H H Ph Me 9- 118 Ph Ph H H H H H H H H Me 9-119 Ph Ph H H Me H H H H H Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9- 120 Ph Ph H H H Me H H H H Me 9- 121 Ph Ph H H H H Me H H H Me 9- 122 Ph Ph H H H H H Me H H Me 9- 123 Ph Ph H H H H H H Me H Me 9- 124 Ph Ph H H H H H H H Me Me 9- 125 Ph Ph H H Ph H H H H H Me 9- 126 Ph Ph H H H Ph H H H H Me 9- 127 Ph Ph H H H H Ph H H H Me 9- 128 Ph Ph H H H H H Ph H H Me 9- 129 Ph Ph H H H H H H Ph H Me 9- 130 Ph Ph H H H H H H H Ph Me
9- 131 Me H Ph H H H H H H H Me 9- 132 Me H Ph H Me H H H H H Me 9- 133 Me H Ph H H Me H H H H Me 9- 134 Me H Ph H H H Me H H H Me 9- 135 Me H Ph H H H H Me H H Me 9- 136 Me H Ph H H H H H Me H Me 9- 137 Me H Ph H H H H H H Me Me 9- 138 Me H Ph H Ph H H H H H Me 9- 139 Me H Ph H H Ph H H H H Me 9- 140 Me H Ph H H H Ph H H H Me 9- 141 Me H Ph H H H H Ph H H Me 9- 142 Me H Ph H H H H H Ph H Me 9- 143 Me H Ph H H H H H H Ph Me 9- 144 Ph H Ph H H H H H H H Me 9- 145 Ph H Ph H Me H H H H H Me 9- 146 Ph H Ph H H Me H H H H Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9- 147 Ph H Ph H H H Me H H H Me 9- 148 Ph H Ph H H H H Me H H Me 9- 149 Ph H Ph H H H H H Me H Me 9- 150 Ph H Ph H H H H H H Me Me 9- 151 Ph H Ph H Ph H H H H H Me 9- 152 Ph H Ph H H Ph H H H H Me 9- 153 Ph H Ph H H H Ph H H H Me 9- 154 Ph H Ph H H H H Ph H H Me 9- 155 Ph H Ph H H H H H Ph H Me 9- 156 Ph H Ph H H H H H H Ph Me
9- 157 Me H H Ph H H H H H H Me 9- 158 Me H H Ph Me H H H H H Me 9- 159 Me H H Ph H Me H H H H Me 9- 160 Me H H Ph H H Me H H H Me 9- 161 Me H H Ph H H H Me H H Me 9- 162 Me H H Ph H H H H Me H Me 9- 163 Me H H Ph H H H H H Me Me 9- 164 Me H H Ph Ph H H H H H Me 9- 165 Me H H Ph H Ph H H H H Me 9- 166 Me H H Ph H H Ph H H H Me 9- 167 Me H H Ph H H H Ph H H Me 9- 168 Me H H Ph H H H H Ph H Me 9- 169 Me H H Ph H H H H H Ph Me 9- 170 Ph H H Ph H H H H H H Me 9- 171 Ph H H Ph Me H H H H H Me 9- 172 Ph H H Ph H Me H H H H Me 9- 173 Ph H H Ph H H Me H H H Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9-174 Ph H H Ph H H H Me H H Me 9-175 Ph H H Ph H H H H Me H Me 9- 176 Ph H H Ph H H H H H Me Me 9-177 Ph H H Ph Ph H H H H H Me 9-178 Ph H H Ph H Ph H H H H Me 9-179 Ph H H Ph H H Ph H H H Me 9-180 Ph H H Ph H H H Ph H H Me 9- 181 Ph H H Ph H H H H Ph H Me 9- 182 Ph H H Ph H H H H H Ph Me
Table 10
Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 10-1 Me H H H H H H H H H H H 10-2 Me H H H Me H H H H H H H 10-3 Me H H H H Me H H H H H H 10-4 Me H H H H H Me H H H H H 10-5 Me H H H H H H Me H H H H 10-6 Me H H H H H H H Me H H H 10-7 Me H H H H H H H H Me H H 10-8 Me H H H H H H H H H Me H 10-9 Me H H H H H H H H H H Me 10-10 Me H H H Ph H H H H H H H 10-11 Me H H H H Ph H H H H H H 10-12 Me H H H H H Ph H H H H H 10-13 Me H H H H H H Ph H H H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 10- 14 Me H H H H H H H Ph H H H 10-15 Me H H H H H H H H Ph H H 10-16 Me H H H H H H H H H Ph H 10-17 Me H H H H H H H H H H Ph 10- 18 Ph H H H H H H H H H H H 10- 19 Ph H H H Me H H H H H H H 10-20 Ph H H H H Me H H H H H H 10.- 21 Ph H H H H H Me H H H H H 10-22 Ph H H H H H H Me H H H H 10-23 Ph H H H H H H H Me H H H 10-24 Ph H H H H H H H H Me H H 10-25 Ph H H H H H H H H H Me H 10-26 Ph H H H H H H H H H H Me 10-27 Ph H H H Ph H H H H H H H 10-28 Ph H H H H Ph H H H H H H 10-29 Ph H H H H H Ph H H H H H 10-30 Ph H H H H H H Ph H H H H 10-31 Ph H H H H H H H Ph H H H 10-32 Ph H H H H H H H H Ph H H 10-33 Ph H H H H H H H H H Ph H 10-34 Ph H H H H H H H H H H Ph
10-35 Me Me H H H H H H H H H H 10-36 Me Me H H Me H H H H H H H 10-37 Me Me H H H Me H H H H H H 10-38 Me Me H H H H Me H H H H H 10-39 Me Me H H H H H Me H H H H 10-40 Me Me H H H H H H Me H H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 RbS 10-41 Me Me H H H H H H H Me H H 10-42 Me Me H H H H H H H H Me H 10-43 Me Me H H H H H H H H H Me 10-44 Me Me H H Ph H H H H H H H 10-45 Me Me H H H Ph H H H H H H 10-46 Me Me H H H H Ph H H H H H 10-47 Me Me H H H H H Ph H H H H 10-48 Me Me H H H H H H Ph H H H 10-49 Me Me H H H H H H H Ph H H 10-50 Me Me H H H H H H H H Ph H 10-51 Me Me H H H H H H H H H Ph 10-52 Ph Me H H H H H H H H H H 10-53 Ph Me H H Me H H H H H H H 10-54 Ph Me H H H Me H H H H H H 10-55 Ph Me H H H H Me H H H H H 10-56 Ph Me H H H H H Me H H H H 10-57 Ph Me H H H H H H Me H H H 10-58 Ph Me H H H H H H H Me H H 10-59 Ph Me H H H H H H H H Me H 10-60 Ph Me H H H H H H H H H Me 10-61 Ph Me H H Ph H H H H H H H 10-62 Ph Me H H H Ph H H H H H H 10-63 Ph Me H H H H Ph H H H H H 10-64 Ph Me H H H H H Ph H H H H 10-65 Ph Me H H H H H H Ph H H H 10-66 Ph Me H H H H H H H Ph H H 10-67 Ph Me H H H H H H H H Ph H 10-68 Ph Me H H H H H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8
10-69 Me H Me H H H H H H H H H 10-70 Me H Me H Me H H H H H H H 10-71 Me H Me H H Me H H H H H H 10-72 Me H Me H H H Me H H H H H 10-73 Me H Me H H H H Me H H H H 10-74 Me H Me H H H H H Me H H H 10-75 Me H Me H H H H H H Me H H 10-76 Me H Me H H H H H H H Me ' H 10-77 Me H Me H H H H H H H H Me 10-78 Me H Me H Ph H H H H H H H 10-79 Me H Me H H Ph H H H H H H 10-80 Me H Me H H H Ph H H H H H 10-81 Me H Me H H H H Ph H H H H 10-82 Me H. Me H H H H H Ph H H H 10-83 Me H Me H H H H H H Ph H H 10-84 Me H Me H H H H H H H Ph H 10-85 Me H Me H H H H H H H H Ph 10-86 Ph H Me H H H H H H H H H 10-87 Ph H Me H Me H H H H H H H 10-88 Ph H Me H H Me H H H H H H 10-89 Ph H Me H H H Me H H H H H 10-90 Ph H Me H H H H Me H H H H 10-91 Ph H Me H H H H H Me H H H 10-92 Ph H Me H H H H H H Me H H 10-93 Ph H Me H H H H H H H Me H 10-94 Ph H Me H H H H H H H H Me 10-95 Ph H Me H Ph H H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 10- 96 Ph H Me H H Ph H H H H H H 10- 97 Ph H Me H H H Ph H H H H H 10- 98 Ph H Me H H H H Ph H H H H 10- 99 Ph H Me H H H H H Ph H H H 10- 100 Ph H Me H H H H H H Ph H H 10- 101 Ph H Me H H H H H H H Ph H 10- 102 Ph H Me H H H H H H H H Ph
10- 103 Me H H Me H H H H H H H H 10- 104 Me H H Me Me H H H H H H H 10- 105 Me H H Me H Me H H H H H H 10- 106 Me H H Me H H Me H H H H H 10- 107 Me H H Me H H H Me H H H H 10- 108 Me H H Me H H H H Me H H H 10- 109 Me H H Me H H H H H Me H H 10- 110 Me H H Me H H H H H H Me H 10- 111 Me H H Me H H H H H H H Me 10- 112 Me H H Me Ph H H H H H H H 10- 113 Me H H Me H Ph H H H H H H 10- 114 Me H H Me H H Ph H H H H H 10- 115 Me H H Me H H H Ph H H H H 10- 116 Me H H Me H H H H Ph H H H 10- 117 Me H H Me H H H H H Ph H H 10- 118 Me H H Me H H H H H H Ph H 10- 119 Me H H Me H H H H H H H Ph 10- 120 Ph H H Me H H H H H H H H 10- 121 Ph H H Me Me H H H H H H H 10- 122 Ph H H Me H Me H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 10- 123 Ph H H Me H H Me H H H H H 10- 124 Ph H H Me H H H Me H H H H 10- 125 Ph H H Me H H H H Me H H H 10- 126 Ph H H Me H H H H H Me H H 10- 127 Ph H H Me H H H H H H Me H 10- 128 Ph H H Me H H H H H H H Me 10- 129 Ph H H Me Ph H H H H H H H 10- 130 Ph H H Me H Ph H H H H H H 10- 131 Ph H H Me H H Ph H H H H H 10- 132 Ph H H Me H H H Ph H H H H 10- 133 Ph H H Me H H H H Ph H H H 10- 134 Ph H H Me H H H H H Ph H H 10- 135 Ph H H Me H H H H H H Ph H 10- 136 Ph H H Me H H H H H H H Ph
10- 137 Me Ph H H H H H H H H H H 10- 138 Me Ph H H Me H H H H H H H 10- 139 Me Ph H H H Me H H H H H H 10- 140 Me Ph H H H H Me H H H H H 10- 141 Me Ph H H H H H Me H H H H 10- 142 Me Ph H H H H H H Me H H H 10- 143 Me Ph H H H H H H H Me H H 10- 144 Me Ph H H H H H H H H Me H 10- 145 Me Ph H H H H H H H H H Me 10- 146 Me Ph H H Ph H H H H H H H 10- 147 Me Ph H H H Ph H H H H H H 10- 148 Me Ph H H H H Ph H H H H H 10- 149 Me Ph H H H H H Ph H H H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 10- 150 Me Ph H H H H H H Ph H H H 10- 151 Me Ph H H H H H H H Ph H H 10- 152 Me Ph H H H H H H H H Ph H 10- 153 Me Ph H H H H H H H H H Ph 10- 154 Ph Ph H H H H H H H H H H 10- 155 Ph Ph H H Me H H H H H H H 10- 156 Ph Ph H H H Me H H H H H H 10- 157 Ph Ph H H H H Me H H H H H 10- 158 Ph Ph H H H H H Me H H H H 10- 159 Ph Ph H H H H H H Me H H H 10- 160 Ph Ph H H H H H H H Me H H 10- 161 Ph Ph H H H H H H H H Me H 10- 162 Ph Ph H H H H H H H H H Me 10- 163 Ph Ph H H Ph H H H H H H H 10- 164 Ph Ph H H H Ph H H H H H H 10- 165 Ph Ph H H H H Ph H H H H H 10- 166 Ph Ph H H H H H Ph H H H H 10- 167 Ph Ph H H H H H H Ph H H H 10- 168 Ph Ph H H H H H H H Ph H H 10- 169 Ph Ph H H H H H H H H Ph H 10- 170 Ph Ph H H H H H H H H H Ph
10- 171 Me H Ph H H H H H H H H H 10- 172 Me H Ph H Me H H H H H H H 10- 173 Me H Ph H H Me H H H H H H 10- 174 Me H Ph H H H Me H H H H H 10- 175 Me H Ph H H H H Me H H H H 10- 176 Me H Ph H H H H H Me H H H
Figure imgf000183_0001
Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8
10- 205 Me H H Ph H H H H H H H H 10- 206 Me H H Ph Me H H H H H H H 10- 207 Me H H Ph H Me H H H H H H 10- 208 Me H H Ph H H Me H H H H H 10- 209 Me H H Ph H H H Me H H H H 10- 210 Me H H Ph H H H H Me H H H 10- 211 Me H H Ph H H H H H Me H H 10- 212 Me H H Ph H H H H H H Me H 10- 213 Me H H Ph H H H H H H H Me 10- 214 Me H H Ph Ph H H H H H H H 10- 215 Me H H Ph H Ph H H H H H H 10- 216 Me H H Ph H H Ph H H H H H 10- 217 Me H H Ph H H H Ph H H H H 10- 218 Me H H Ph H H H H Ph H H H 10- 219 Me H H Ph H H H H H Ph H H 10- 220 Me H H Ph H H H H H H Ph H 10- 221 Me H H Ph H H H H H H H Ph 10- 222 Ph H H Ph H H H H H H H H 10- 223 Ph H H Ph Me H H H H H H H 10- 224 Ph H H Ph H Me H H H H H H 10- 225 Ph H H Ph H H Me H H H H H 10- 226 Ph H H Ph H H H Me H H H H 10- 227 Ph H H Ph H H H H Me H H H 10- 228 Ph H H Ph H H H H H Me H H 10- 229 Ph H H Ph H H H H H H Me H 10- 230 Ph H H Ph H H H H H H H Me 10- 231 Ph H H Ph Ph H H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 RbS 10- 232 Ph H H Ph H Ph H H H H H H 10- 233 Ph H H Ph H H Ph H H H H H 10- 234 Ph H H Ph H H H Ph H H H H 10- 235 Ph H H Ph H H H H Ph H H H 10- 236 Ph H H Ph H H H H H Ph H H 10- 237 Ph H H Ph H H H H H H Ph H 10- 238 Ph H H Ph H H H H H H H Ph
Table 11
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 1-1 Me H H H H H H 1-2 Me H H H H Me H 1-3 Me H H H H H Me 1-4 Me H H H H Ph H 1-5 Me H H H H H Ph 1-6 Ph H H H H H H 1-7 Ph H H H H Me H 1-8 Ph H H H H H Me 1-9 Ph H H H H Ph H 1- 10 Ph H H H H H Ph
11-11 Me Me H H H H H 11-12 Me Me H H H Me H 11-13 Me Me H H H H Me 11-14 Me Me H H H Ph H 11-15 Me Me H H H H Ph 11-16 Ph Me H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 11-17 Ph Me H H H Me H 11-18 Ph Me H H H H Me 11-19 Ph Me H H H Ph H 11-20 Ph Me H H H H Ph
11-21 Me H Me H H H H 11-22 Me H Me H H Me H 11-23 Me H Me H H H Me 11-24 Me H Me H H Ph H 11-25 Me H Me H H H Ph 11-26 Ph H Me H H H H 11-27 Ph H Me H H Me H 11-28 Ph H Me H H H Me 11-29 Ph H Me H H Ph H 11-30 Ph H Me H H H Ph
11-31 Me H H Me H H H 11-32 Me H H Me H Me H 11-33 Me H H Me H H Me 11-34 Me H H Me H Ph H 11-35 Me H H Me H H Ph 11-36 Ph H H Me H H H 11-37 Ph H H Me H Me H 11-38 Ph H H Me H H Me 11-39 Ph H H Me H Ph H 11-40 Ph H H Me H H Ph
11-41 Me H H H Me H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 11-42 Me H H H Me Me H 11-43 Me H H H Me H Me 11-44 Me H H H Me Ph H 11-45 Me H H H Me H Ph 11-46 Ph H H H Me H H 11-47 Ph H H H Me Me H 11-48 Ph H H H Me H Me 11-49 Ph H H H Me Ph H 11-50 Ph H H H Me H Ph
11-51 Me Ph H H H H H 11-52 Me Ph H H H Me H 11-53 Me Ph H H H H Me 11-54 Me Ph H H H Ph H 11-55 Me Ph H H H H Ph 11-56 Ph Ph H H H H H 11-57 Ph Ph H H H Me H 11-58 Ph Ph H H H H Me 11-59 Ph Ph H H H Ph H 11-60 Ph Ph H H H H Ph
11-61 Me H Ph H H H H 11-62 Me H Ph H H Me H 11-63 Me H Ph H H H Me 11-64 Me H Ph H H Ph H 11-65 Me H Ph H H H Ph 11-66 Ph H Ph H H H H 11-67 Ph H Ph H H Me H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 11-68 Ph H Ph H H H Me 11-69 Ph H Ph H H Ph H 11-70 Ph H Ph H H H Ph
11-71 Me H H Ph H H H 11-72 Me H H Ph H Me H 11-73 Me H H Ph H H Me 11-74 Me H H Ph H Ph H 11-75 Me H H Ph H H Ph 11-76 Ph H H Ph H H H 11-77 Ph H H Ph H Me H 11-78 Ph H H Ph H H Me 11-79 Ph H H Ph H Ph H 11-80 Ph H H Ph H H Ph
11-81 Me H H H Ph H H 11-82 Me H H H Ph Me H 11-83 Me H H H Ph H Me 11-84 Me H H H Ph Ph H 11-85 Me H H H Ph H Ph 11-86 Ph H H H Ph H H 11-87 Ph H H H Ph Me H 11-88 Ph H H H Ph H Me 11-89 Ph H H H Ph Ph H 11-90 Ph H H H Ph H Ph
Table 12
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 12-1 Me H H H H H H H H 12-2 Me H H H H Me H H H 12-3 Me H H H H H Me H H 12-4 Me H H H H H H Me H 12-5 Me H H H H H H H Me 12-6 Me H H H H Ph H H H 12-7 Me H H H H H Ph H H 12-8 Me H H H H H H Ph H 12-9 Me H H H H H H H Ph 12-10 Ph H H H H H H H H 12-11 Ph H H H H Me H H H 12-12 Ph H H H H H Me H H 12-13 Ph H H H H H H Me H 12-14 Ph H H H H H H H Me 12-15 Ph H H H H Ph H H H 12-16 Ph H H H H H Ph H H 12- 17 Ph H H H H H H Ph H 12-18 Ph H H H H H H H Ph
12- 19 Me Me H H H H H H H 12-20 Me Me H H H Me H H H 12-21 Me Me H H H H Me H H 12-22 Me Me H H H H H Me H 12-23 Me Me H H H H H H Me 12-24 Me Me H H H Ph H H H 12-25 Me Me H H H H Ph H H 12-26 Me Me H H H H H Ph H 12-27 Me Me H H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 12-28 Ph Me H H H H H H H 12-29 Ph Me H H H Me H H H 12-30 Ph Me H H H H Me H H 12-31 Ph Me H H H H H Me H 12-32 Ph Me H H H H H H Me 12-33 Ph Me H H H Ph H H H 12-34 Ph Me H H H H Ph H H 12-35 Ph Me H H H H H Ph H 12-36 Ph Me H H H H H H Ph
12-37 Me H Me H H H H H H 12-38 Me H Me H H Me H H H 12-39 Me H Me H H H Me H H 12-40 Me H Me H H H H Me H 12-41 Me H Me H H H H H Me 12-42 Me H Me H H Ph H H H 12-43 Me H Me H H H Ph H H 12-44 Me H Me H H H H Ph H 12-45 Me H Me H H H H H Ph 12-46 Ph H Me H H H H H H 12-47 Ph H Me H H Me H H H 12-48 Ph H Me H H H Me H H 12-49 Ph H Me H H H H Me H 12-50 Ph H Me H H H H H Me 12-51 Ph H Me H H Ph H H H 12-52 Ph H Me H H H Ph H H 12-53 Ph H Me H H H ' H Ph H 12-54 Ph H Me H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4
12-55 Me H H Me H H H H H 12-56 Me H H Me H Me H H H 12-57 Me H H Me H H Me H H 12-58 Me H H Me H H H Me H 12-59 Me H H Me H H H H Me 12-60 Me H H Me H Ph H H H 12-61 Me H H Me H H Ph H H 12-62 Me H H Me H H H Ph H 12-63 Me H H Me H H H H Ph 12-64 Ph H H Me H H H H H 12-65 Ph H H Me H Me H H H 12-66 Ph H H Me H H Me H H 12-67 Ph H H Me H H H Me H 12-68 Ph H H Me H H H H Me 12-69 Ph H H Me H Ph H H H 12-70 Ph H H Me H H Ph H H 12-71 Ph H H Me H H H Ph H 12-72 Ph H H Me H H H H Ph
12-73 Me H H H Me H H H H 12-74 Me H H H Me Me H H H 12-75 Me H H H Me H Me H H 12-76 Me H H H Me H H Me H 12-77 Me H H H Me H H H Me 12-78 Me H H H Me Ph H H H 12-79 Me H H H Me H Ph H H 12-80 Me H H H Me H H Ph H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 12-81 Me H H H Me H H H Ph 12-82 Ph H H H Me H H H H 12-83 Ph H H H Me Me H H H 12-84 Ph H H H Me H Me H H 12-85 Ph H H H Me H H Me H 12-86 Ph H H H Me H H H Me 12-87 Ph H H H Me Ph H H H 12-88 Ph H H H Me H Ph H H 12-89 Ph H H H Me H H Ph H 12-90 Ph H H H Me H H H Ph
12-91 Me Ph H H H H H H H 12-92 Me Ph H H H Me H H H 12-93 Me Ph H H H H Me H H 12-94 Me Ph H H H H H Me H 12-95 Me Ph H H H H H H Me 12-96 Me Ph H H H Ph H H H 12-97 Me Ph H H H H Ph H H 12-98 Me Ph H H H H H Ph H 12-99 Me Ph H H H H H H Ph 12- 100 Ph Ph H H H H H H H 12- 101 Ph Ph H H H Me H H H 12- 102 Ph Ph H H H H Me H H 12- 103 Ph Ph H H H H H Me H 12- 104 Ph Ph H H H H H H Me 12- 105 Ph Ph H H H Ph H H H 12- 106 Ph Ph H H H H Ph H H 12- 107 Ph Ph H H H H H Ph H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 12- 108 Ph Ph H H H H H H Ph
12- 109 Me H Ph H H H H H H 12- 110 Me H Ph H H Me H H H 12- 111 Me H Ph H H H Me H H 12- 112 Me H Ph H H H H Me H 12- 113 Me H Ph H H H H H Me 12- 114 Me H Ph H H Ph H H H 12- 115 Me H Ph H H H Ph H H 12- 116 Me H Ph H H H H Ph H 12- 117 Me H Ph H H H H H Ph 12- 118 Ph H Ph H H H H H H 12- 119 Ph H Ph H H Me H H H 12- 120 Ph H Ph H H H Me H H 12- 121 Ph H Ph H H H H Me H 12- 122 Ph H Ph H H H H H Me 12- 123 Ph H Ph H H Ph H H H 12- 124 Ph H Ph H H H Ph H H 12- 125 Ph H Ph H H H H Ph H 12- 126 Ph H Ph H H H H H Ph
12- 127 Me H H Ph H H H H H 12- 128 Me H H Ph H Me H H H 12- 129 Me H H Ph H H Me H H 12- 130 Me H H Ph H H H Me H 12- 131 Me H H Ph H H H H Me 12- 132 Me H H Ph H Ph H H H 12- 133 Me H H Ph H H Ph H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 12- 134 Me H H Ph H H H Ph H 12- 135 Me H H Ph H H H H Ph 12- 136 Ph H H Ph H H H H H 12- 137 Ph H H Ph H Me H H H 12- 138 Ph H H Ph H H Me H H 12- 139 Ph H H Ph H H H Me H 12- 140 Ph H H Ph H H H H Me 12- 141 Ph H H Ph H Ph H H H 12- 142 Ph H H Ph H H Ph H H 12- 143 Ph H H Ph H H H Ph H 12- 144 Ph H H Ph H H H H Ph
12- 145 Me H H H Ph H H H H 12- 146 Me H H H Ph Me H H H 12- 147 Me H H H Ph H Me H H 12- 148 Me H H H Ph H H Me H 12- 149 Me H H H Ph H H H Me 12- 150 Me H H H Ph Ph H H H 12- 151 Me H H H Ph H Ph H H 12- 152 Me H H H Ph H H Ph H 12- 153 Me H H H Ph H H H Ph 12- 154 Ph H H H Ph H H H H 12- 155 Ph H H H Ph Me H H H 12- 156 Ph H H H Ph H Me H H 12- 157 Ph H H H Ph H H Me H 12- 158 Ph H H H Ph H H H Me 12- 159 Ph H H H Ph Ph H H H 12- 160 Ph H H H Ph H Ph H H
Figure imgf000195_0001
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 13-23 Ph H H H H H H Ph H H H 13-24 Ph H H H H H H H Ph H H 13-25 Ph H H H H H H H H Ph H 13-26 Ph H H H H H H H H H Ph
13-27 Me Me H H H H H H H H H 13-28 Me Me H H H Me H H H H H 13-29 Me Me H H H H Me H H H H 13-30 Me Me H H H H H Me H H H 13-31 Me Me H H H H H H Me H H 13-32 Me Me H H H H H H H Me H 13-33 Me Me H H H H H H H H Me 13-34 Me Me H H H Ph H H H H H 13-35 Me Me H H H H Ph H H H H 13-36 Me Me H H H H H Ph H H H 13-37 Me Me H H H H H H Ph H H 13-38 Me Me H H H H H H H Ph H 13-39 Me Me H H H H H H H H Ph 13-40 Ph Me H H H H H H H H H 13-41 Ph Me H H H Me H H H H H 13-42 Ph Me H H H H Me H H H H 13-43 Ph Me H H H H H Me H H H 13-44 Ph Me H H H H H H Me H H 13-45 Ph Me H H H H H H H Me H 13-46 Ph Me H H H H H H H H Me 13-47 Ph Me H H H Ph H H H H H 13-48 Ph Me H H H H Ph H H H H 13-49 Ph Me H H H H H Ph H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 13-50 Ph Me H H H H H H Ph H H 13-51 Ph Me H H H H H H H Ph H 13-52 Ph Me H H H H H H H H Ph
13-53 Me H Me H H H H H H H H 13-54 Me H Me H H Me H H H H H 13-55 Me H Me H H H Me H H H H 13-56 Me H Me H H H H Me H H H 13-57 Me H Me H H H H H Me H H 13-58 Me H Me H H H H H H Me H 13-59 Me H Me H H H H H H H Me 13-60 Me H Me H H Ph H H H H H 13-61 Me H Me H H H Ph H H H H 13-62 Me H Me H H H H Ph H H H 13-63 Me H Me H H H H H Ph H H 13-64 Me H Me H H H H H H Ph H 13-65 Me H Me H H H H H H H Ph 13-66 Ph H Me H H H H H H H H 13-67 Ph H Me H H Me H H H H H 13-68 Ph H Me H H H Me H H H H 13-69 Ph H Me H H H H Me H H H 13-70 Ph H Me H H H H H Me H H 13-71 Ph H Me H H H H H H Me H 13-72 Ph H Me H H H H H H H Me 13-73 Ph H Me H H Ph H H H H H 13-74 Ph H Me H H H Ph H H H H 13-75 Ph H Me H H H H Ph H H H 13-76 Ph H Me H H H H H Ph H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 13-77 Ph H Me H H H H H H Ph H 13-78 Ph H Me H H H H H H H Ph
13-79 Me H H Me H H H H H H H 13-80 Me H H Me H Me H H H H H 13-81 Me H H Me H H Me H H H H 13-82 Me H H Me H H H Me H H H 13-83 Me H H Me H H H H Me H H 13-84 Me H H Me H H H H H Me H 13-85 Me H H Me H H H H H H Me 13-86 Me H H Me H Ph H H H H H 13-87 Me H H Me H H Ph H H H H 13-88 Me H H Me H H H Ph H H H 13-89 Me H H Me H H H H Ph H H 13-90 Me H H Me H H H H H Ph H 13-91 Me H H Me H H H H H H Ph 13-92 Ph H H Me H H H H H H H 13-93 Ph H H Me H Me H H H H H 13-94 Ph H H Me H H Me H H H H 13-95 Ph H H Me H H H Me H H H 13-96 Ph H H Me H H H H Me H H 13-97 Ph H H Me H H H H H Me H 13-98 Ph H H Me H H H H H H Me 13-99 Ph H H Me H Ph H H H H H 13- 100 Ph H H Me H H Ph H H H H 13- 101 Ph H H Me H H H Ph H H H 13- 102 Ph H H Me H H H H Ph H H 13- 103 Ph H H Me H H H H H Ph H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 13- 104 Ph H H Me H H H H H H Ph
13- 105 Me H H H Me H H H H H H 13- 106 Me H H H Me Me H H H H H 13- 107 Me H H H Me H Me H H H H 13- 108 Me H H H Me H H Me H H H 13- 109 Me H H H Me H H H Me H H 13- 110 Me H H H Me H H H H Me H 13- 111 Me H H H Me H H H H H Me 13- 112 Me H H H Me Ph H H H H H 13- 113 Me H H H Me H Ph H H H H 13- 114 Me H H H Me H H Ph H H H 13- 115 Me H H H Me H H H Ph H H 13- 116 Me H H H Me H H H H Ph H 13- 117 Me H H H Me H H H H H Ph 13- 118 Ph H H H Me H H H H H H 13- 119 Ph H H H Me Me H H H H H 13- 120 Ph H H H Me H Me H H H H 13- 121 Ph H H H Me H H Me H H H 13- 122 Ph H H H Me H H H Me H H 13- 123 Ph H H H Me H H H H Me H 13- 124 Ph H H H Me H H H H H Me 13- 125 Ph H H H Me Ph H H H H H 13- 126 Ph H H H Me H Ph H H H H 13- 127 Ph H H H Me H H Ph H H H 13- 128 Ph H H H Me H H H Ph H H 13- 129 Ph H H H Me H H H H Ph H 13- 130 Ph H H H Me H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6
13- 131 Me Ph H H H H H H H H H 13- 132 Me Ph H H H Me H H H H H 13- 133 Me Ph H H H H Me H H H H 13- 134 Me Ph H H H H H Me H H H 13- 135 Me Ph H H H H H H Me H H 13- 136 Me Ph H H H H H H H Me H 13- 137 Me Ph H H H H H H H H Me 13- 138 Me Ph H H H Ph H H H H H 13- 139 Me Ph H H H H Ph H H H H 13- 140 Me Ph H H H H H Ph H H H 13- 141 Me Ph H H H H H H Ph H H 13- 142 Me Ph H H H H H H H Ph H 13- 143 Me Ph H H H H H H H H Ph 13- 144 Ph Ph H H H H H H H H H 13- 145 Ph Ph H H H Me H H H H H 13- 146 Ph Ph H H H H Me H H H H 13- 147 Ph Ph H H H H H Me H H H 13- 148 Ph Ph H H H H H H Me H H 13- 149 Ph Ph H H H H H H H Me H 13- 150 Ph Ph H H H H H H H H Me 13- 151 Ph Ph H H H Ph H H H H H 13- 152 Ph Ph H H H H Ph H H H H 13- 153 Ph Ph H H H H H Ph H H H 13- 154 Ph Ph H H H H H H Ph H H 13- 155 Ph Ph H H H H H H H Ph H 13- 156 Ph Ph H H H H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 13- 157 Me H Ph H H H H H H H H 13- 158 Me H Ph H H Me H H H H H 13- 159 Me H Ph H H H Me H H H H 13- 160 Me H Ph H H H H Me H H H 13- 161 Me H Ph H H H H H Me H H 13- 162 Me H Ph H H H H H H Me H 13- 163 Me H Ph H H H H H H H Me 13- 164 Me H Ph H H Ph H H H H H 13- 165 Me H Ph H H H Ph H H H H 13- 166 Me H Ph H H H H Ph H H H 13- 167 Me H Ph H H H H H Ph H H 13- 168 Me H Ph H H H H H H Ph H 13- 169 Me H Ph H H H H H H H Ph 13- 170 Ph H Ph H H H H H H H H 13- 171 Ph H Ph H H Me H H H H H 13- 172 Ph H Ph H H H Me H H H H 13- 173 Ph H Ph H H H H Me H H H 13- 174 Ph H Ph H H H H H Me H H 13- 175 Ph H Ph H H H H H H Me H 13- 176 Ph H Ph H H H H H H H Me 13- 177 Ph H Ph H H Ph H H H H H 13- 178 Ph H Ph H H H Ph H H H H 13- 179 Ph H Ph H H H H Ph H H H 13- 180 Ph H Ph H H H H H Ph H H 13- 181 Ph H Ph H H H H H H Ph H 13- 182 Ph H Ph H H H H H H H Ph
13- 183 Me H H Ph H H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 13- 184 Me H H Ph H Me H H H H H 13- 185 Me H H Ph H H Me H H H H 13- 186 Me H H Ph H H H Me H H H 13- 187 Me H H Ph H H H H Me H H 13- 188 Me H H Ph H H H H H Me H 13- 189 Me H H Ph H H H H H H Me 13- 190 Me H H Ph H Ph H H H H H 13- 191 Me H H Ph H H Ph H H H H 13- 192 Me H H Ph H H H Ph H H H 13- 193 Me H H Ph H H H H Ph H H 13- 194 Me H H Ph H H H H H Ph H 13- 195 Me H H Ph H H H H H H Ph 13- 196 Ph H H Ph H H H H H H H 13- 197 Ph H H Ph H Me H H H H H 13- 198 Ph H H Ph H H Me H H H H 13- 199 Ph H H Ph H H H Me H H H 13- 200 Ph H H Ph H H H H Me H H 13- 201 Ph H H Ph H H H H H Me H 13- 202 Ph H H Ph H H H H H H Me 13- 203 Ph H H Ph H Ph H H H H H 13- 204 Ph H H Ph H H Ph H H H H 13- 205 Ph H H Ph H H H Ph H H H 13- 206 Ph H H Ph H H H H Ph H H 13- 207 Ph H H Ph H H H H H Ph H 13- 208 Ph H H Ph H H H H H H Ph
13- 209 Me H H H Ph H H H H H H 13- 210 Me H H H Ph Me H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 13- 211 Me H H H Ph H Me H H H H 13- 212 Me H H H Ph H H Me H H H 13- 213 Me H H H Ph H H H Me H H 13- 214 Me H H H Ph H H H H Me H 13- 215 Me H H H Ph H H H H H Me 13- 216 Me H H H Ph Ph H H H H H 13- 217 Me H H H Ph H Ph H H H H 13- 218 Me H H H Ph H H Ph H H H 13- 219 Me H H H Ph H H H Ph H H 13- 220 Me H H H Ph H H H H Ph H 13- 221 Me H H H Ph H H H H H Ph 13- 222 Ph H H H Ph H H H H H H 13- 223 Ph H H H Ph Me H H H H H 13- 224 Ph H H H Ph H Me H H H H 13- 225 Ph H H H Ph H H Me H H H 13- 226 Ph H H H Ph H H H Me H H 13- 227 Ph H H H Ph H H H H Me H 13- 228 Ph H H H Ph H H H H H Me 13- 229 Ph H H H Ph Ph H H H H H 13- 230 Ph H H H Ph H Ph H H H H 13- 231 Ph H H H Ph H H Ph H H H 13- 232 Ph H H H Ph H H H Ph H H 13- 233 Ph H H H Ph H H H H Ph H 13- 234 Ph H H H Ph H H H H H Ph
Table 14
Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 14-1 Me H H H H H H H H H H Me 14-2 Me H H H H Me H H H H H Me 14-3 Me H H H H H Me H H H H Me 14-4 Me H H H H H H Me H H H Me 14-5 Me H H H H H H H Me H H Me 14-6 Me H H H H H H H H Me H Me 14-7 Me H H H H H H H H H Me Me 14-8 Me H H H H Ph H H H H H Me 14-9 Me H H H H H Ph H H H H Me 14-10 Me H H H H H H Ph H H H Me 14-11 Me H H H H H H H Ph H H Me 14-12 Me H H H H H H H H Ph H Me 14-13 Me H H H H H H H H H Ph Me 14-14 Ph H H H H H H H H H H Me 14-15 Ph H H H H Me H H H H H Me 14-16 Ph H H H H H Me H H H H Me 14-17 Ph H H H H H H Me H H H Me 14-18 Ph H H H H H H H Me H H Me 14-19 Ph H H H H H H H H Me H Me 14-20 Ph H H H H H H H H H Me Me 14-21 Ph H H H H Ph H H H H H Me 14-22 Ph H H H H H Ph H H H H Me 14-23 Ph H H H H H H Ph H H H Me 14-24 Ph H H H H H H H Ph H H Me 14-25 Ph H H H H H H H H Ph H Me 14-26 Ph H H H H H H H H H Ph Me
14- 27 Me Me H H H H H H H H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 14-28 Me Me H H H Me H H H H H Me 14-29 Me Me H H H H Me H H H H Me 14-30 Me Me H H H H H Me H H H Me 14-31 Me Me H H H H H H Me H H Me 14-32 Me Me H H H H H H H Me H Me 14-33 Me Me H H H H H H H H Me Me 14-34 Me Me H H H Ph H H H H H Me 14-35 Me Me H H H H Ph H H H H Me 14-36 Me Me H H H H H Ph H H H Me 14-37 Me Me H H H H H H Ph H H Me 14-38 Me Me H H H H H H H Ph H Me 14-39 Me Me H H H H H H H H Ph Me 14-40 Ph Me H H H H H H H H H Me 14-41 Ph Me H H H Me H H H H H Me 14-42 Ph Me H H H H Me H H H H Me 14-43 Ph Me H H H H H Me H H H Me 14-44 Ph Me H H H H H H Me H H Me 14-45 Ph Me H H H H H H H Me H Me 14-46 Ph Me H H H H H H H H Me Me 14-47 Ph Me H H H Ph H H H H H Me 14-48 Ph Me H H H H Ph H H H H Me 14-49 Ph Me H H H H H Ph H H H Me 14-50 Ph Me H H H H H H Ph H H Me 14-51 Ph Me H H H H H H H Ph H Me 14-52 Ph Me H H H H H H H H Ph Me
14-53 Me H Me H H H H H H H H Me 14-54 Me H Me H H Me H H H H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 14-55 Me H Me H H H Me H H H H Me 14-56 Me H Me H H H H Me H H H Me 14-57 Me H Me H H H H H Me H H Me 14-58 Me H Me H H H H H H Me H Me 14-59 Me H Me H H H H H H H Me Me 14-60 Me H Me H H Ph H H H H H Me 14-61 Me H Me H H H Ph H H H H Me 14-62 Me H Me H H H H Ph H H H Me 14-63 Me H Me H H H H H Ph H H Me 14-64 Me H Me H H H H H H Ph H Me 14-65 Me H Me H H H H H H H Ph Me 14-66 Ph H Me H H H H H H H H Me 14-67 Ph H Me H H Me H H H H H Me 14-68 Ph H Me H H H Me H H H H Me 14-69 Ph H Me H H H H Me H H H Me 14-70 Ph H Me H H H H H Me H H Me 14-71 Ph H Me H H H H H H Me H Me 14-72 Ph H Me H H H H H H H Me Me 14-73 Ph H Me H H Ph H H H H H Me 14-74 Ph H Me H H H Ph H H H H Me 14-75 Ph H Me H H H H Ph H H H Me 14-76 Ph H Me H H H H H Ph H H Me 14-77 Ph H Me H H H H H H Ph H Me 14-78 Ph H Me H H H H H H H Ph Me
14-79 Me H H Me H H H H H H H Me 14-80 Me H H Me H Me H H H H H Me 14-81 Me H H Me H H Me H H H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 14-82 Me H H Me H H H Me H H H Me 14-83 Me H H Me H H H H Me H H Me 14-84 Me H H Me H H H H H Me H Me 14-85 Me H H Me H H H H H H Me Me 14-86 Me H H Me H Ph H H H H H Me 14-87 Me H H Me H H Ph H H H H Me 14-88 Me H H Me H H H Ph H H H Me 14-89 Me H H Me H H H H Ph H H Me 14-90 Me H H Me H H H H H Ph H Me 14-91 Me H H Me H H H H H H Ph Me 14-92 Ph H H Me H H H H H H H Me 14-93 Ph H H Me H Me H H H H H Me 14-94 Ph H H Me H H Me H H H H Me 14-95 Ph H H Me H H H Me H H H Me 14-96 Ph H H Me H H H H Me H H Me 14-97 Ph H H Me H H H H H Me H Me 14-98 Ph H H Me H H H H H H Me Me 14-99 Ph H H Me H Ph H H H H H Me ■ 14- 100 Ph H H Me H H Ph H H H H Me 14- 101 Ph H H Me H H H Ph H H H Me 14- 102 Ph H H Me H H H H Ph H H Me 14- 103 Ph H H Me H H H H H Ph H Me 14- 104 Ph H H Me H H H H H H Ph Me
14- 105 Me H H H Me H H H H H H Me 14- 106 Me H H H Me Me H H H H H Me 14- 107 Me H H H Me H Me H H H H Me 14- 108 Me H H H Me H H Me H H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 14- 109 Me H H H Me H H H Me H H Me 14- 110 Me H H H Me H H H H Me H Me 14- 111 Me H H H Me H H H H H Me Me 14- 112 Me H H H Me Ph H H H H H Me 14- 113 Me H H H Me H Ph H H H H Me 14- 114 Me H H H Me H H Ph H H H Me 14- 115 Me H H H Me H H H Ph H H Me 14- 116 Me H H H Me H H H H Ph H Me 14- 117 Me H H H Me H H H H H Ph Me 14- 118 Ph H H H Me H H H H H H Me 14- 119 Ph H H H Me Me H H H H H Me 14- 120 Ph H H H Me H Me H H H H Me 14- 121 Ph H H H Me H H Me H H H Me 14- 122 Ph H H H Me H H H Me H H Me 14- 123 Ph H H H Me H H H H Me H Me 14- 124 Ph H H H Me H H H H H Me Me 14- 125 Ph H H H Me Ph H H H H H Me 14- 126 Ph H H H Me H Ph H H H H Me 14- 127 Ph H H H Me H H Ph H H H Me 14- 128 Ph H H H Me H H H Ph H H Me 14- 129 Ph H H H Me H H H H Ph H Me 14- 130 Ph H H H Me H H H H H Ph Me
14- 131 Me Ph H H H H H H H H H Me 14- 132 Me Ph H H H Me H H H H H Me 14- 133 Me Ph H H H H Me H H H H Me 14- 134 Me Ph H H H H H Me H H H Me 14- 135 Me Ph H H H H H H Me H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 14- 136 Me Ph H H H H H H H Me H Me 14- 137 Me Ph H H H H H H H H Me Me 14- 138 Me Ph H H H Ph H H H H H Me 14- 139 Me Ph H H H H Ph H H H H Me 14- 140 Me Ph H H H H H Ph H H H Me 14- 141 Me Ph H H H H H H Ph H H Me 14- 142 Me Ph H H H H H H H Ph H Me 14- 143 Me Ph H H H H H H H H Ph Me 14- 144 Ph Ph H H H H H H H H H Me 14- 145 Ph Ph H H H Me H H H H H Me 14- 146 Ph Ph H H H H Me H H H H Me 14- 147 Ph Ph H H H H H Me H H H Me 14- 148 Ph Ph H H H H H H Me H H Me 14- 149 Ph Ph H H H H H H H Me H Me 14- 150 Ph Ph H H H H H H H H Me Me 14- 151 Ph Ph H H H Ph H H H H H Me 14- 152 Ph Ph H H H H Ph H H H H Me 14- 153 Ph Ph H H H H H Ph H H H Me 14- 154 Ph Ph H H H H H H Ph H H Me 14- 155 Ph Ph H H H H H H H Ph H Me 14- 156 Ph Ph H H H H H H H H Ph Me
14- 157 Me H Ph H H H H H H H H Me 14- 158 Me H Ph H H Me H H H H H Me 14- 159 Me H Ph H H H Me H H H H Me 14- 160 Me H Ph H H H H Me H H H Me 14- 161 Me H Ph H H H H H Me H H Me 14- 162 Me H Ph H H H H H H Me H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 14- 163 Me H Ph H H H H H H H Me Me 14- 164 Me H Ph H H Ph H H H H H Me 14- 165 Me H Ph H H H Ph H H H H Me 14- 166 Me H Ph H H H H Ph H H H Me 14- 167 Me H Ph H H H H H Ph H H Me 14- 168 Me H Ph H H H H H H Ph H Me 14- 169 Me H Ph H H H H H H H Ph Me 14- 170 Ph H Ph H H H H H H H H Me 14- 171 Ph H Ph H H Me H H H H H Me 14- 172 Ph H Ph H H H Me H H H H Me 14- 173 Ph H Ph H H H H Me H H H Me 14- 174 Ph H Ph H H H H H Me H H Me 14- 175 Ph H Ph H H H H H H Me H Me 14- 176 Ph H Ph H H H H H H H Me Me 14- 177 Ph H Ph H H Ph H H H H H Me 14- 178 Ph H Ph H H H Ph H H H H Me 14- 179 Ph H Ph H H H H Ph H H H Me 14- 180 Ph H Ph H H H H H Ph H H Me 14- 181 Ph H Ph H H H H H H Ph H Me 14- 182 Ph H Ph H H H H H H H Ph Me
14- 183 Me H H Ph H H H H H H H Me 14- 184 Me H H Ph H Me H H H H H Me 14- 185 Me H H Ph H H Me H H H H Me 14- 186 Me H H Ph H H H Me H H H Me 14- 187 Me H H Ph H H H H Me H H Me 14- 188 Me H H Ph H H H H H Me H Me 14- 189 Me H H Ph H H H H H H Me Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 14- 190 Me H H Ph H Ph H H H H H Me 14- 191 Me H H Ph H H Ph H H H H Me 14- 192 Me H H Ph H H H Ph H H H Me 14- 193 Me H H Ph H H H H Ph H H Me 14- 194 Me H H Ph H H H H H Ph H Me 14- 195 Me H H Ph H H H H H H Ph Me 14- 196 Ph H H Ph H H H H H H H Me 14- 197 Ph H H Ph H Me H H H H H Me 14- 198 Ph H H Ph H H Me H H H H Me 14- 199 Ph H H Ph H H H Me H H H Me 14- 200 Ph H H Ph H H H H Me H H Me 14- 201 Ph H H Ph H H H H H Me H Me 14- 202 Ph H H Ph H H H H H H Me Me 14- 203 Ph H H Ph H Ph H H H H H Me 14- 204 Ph H H Ph H H Ph H H H H Me 14- 205 Ph H H Ph H H H Ph H H H Me 14- 206 Ph H H Ph H H H H Ph H H Me 14- 207 Ph H H Ph H H H H H Ph H Me 14- 208 Ph H H Ph H H H H H H Ph Me
14- 209 Me H H H Ph H H H H H H Me 14- 210 Me H H H Ph Me H H H H H Me 14- 211 Me H H H Ph H Me H H H H Me 14- 212 Me H H H Ph H H Me H H H Me 14- 213 Me H H H Ph H H H Me H H Me 14- 214 Me H H H Ph H H H H Me H Me 14- 215 Me H H H Ph H H H H H Me Me 14- 216 Me H H H Ph Ph H H H H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 14- 217 Me H H H Ph H Ph H H H H Me 14- 218 Me H H H Ph H H Ph H H H Me 14- 219 Me H H H Ph H H H Ph H H Me 14- 220 Me H H H Ph H H H H Ph H Me 14- 221 Me H H H Ph H H H H H Ph Me 14- 222 Ph H H H Ph H H H H H H Me 14- 223 Ph H H H Ph Me H H H H H Me 14- 224 Ph H H H Ph H Me H H H H Me 14- 225 Ph H H H Ph H H Me H H H Me 14- 226 Ph H H H Ph H H H Me H H Me 14- 227 Ph H H H Ph H H H H Me H Me 14- 228 Ph H H H Ph H H H H H Me Me 14- 229 Ph H H H Ph Ph H H H H H Me 14- 230 Ph H H H Ph H Ph H H H H Me 14- 231 Ph H H H Ph H H Ph H H H Me 14- 232 Ph H H H Ph H H H Ph H H Me 14- 233 Ph H H H Ph H H H H Ph H Me 14- 234 Ph H H H Ph H H H H H Ph Me
Table 15
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 15- 1 Me H H H H H H H H H H H H 15- 2 Me H H H H Me H H H H H H H 15- 3 Me H H H H H Me H H H H H H 15- 4 Me H H H H H H Me H H H H H 15- 5 Me H H H H H H H Me H H H H 15- 6 Me H H H H H H H H Me H H H
Figure imgf000213_0001
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 RbS
15-35 Me Me H H H H H H H H H H H 15-36 Me Me H H H Me H H H H H H H 15-37 Me Me H H H H Me H H H H H H 15-38 Me Me H H H H H Me H H H H H 15-39 Me Me H H H H H H Me H H H H 15-40 Me Me H H H H H H H Me H H H 15-41 Me Me H H H H H H H H Me H H 15-42 Me Me H H H H H H H H H Me H 15-43 Me Me H H H H H H H H H H Me 15-44 Me Me H H H Ph H H H H H H H 15-45 Me Me H H H H Ph H H H H H H 15-46 Me Me H H H H H Ph H H H H H 15-47 Me Me H H H H H H Ph H H H H 15-48 Me Me H H H H H H H Ph H H H 15-49 Me Me H H H H H H H H Ph H H 15-50 Me Me H H H H H H H H H Ph H 15-51 Me Me H H H H H H H H H H Ph 15-52 Ph Me H H H H H H H H H H H 15-53 Ph Me H H H Me H H H H H H H 15-54 Ph Me H H H H Me H H H H H H 15-55 Ph Me H H H H H Me H H H H H 15-56 Ph Me H H H H H H Me H H H H 15-57 Ph Me H H H H H H H Me H H H 15-58 Ph Me H H H H H H H H Me H H 15-59 Ph Me H H H H H H H H H Me H 15-60 Ph Me H H H H H H H H H H Me 15-61 Ph Me H H H Ph H H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 15-62 Ph Me H H H H Ph H H H H H H 15-63 Ph Me H H H H H Ph H H H H H 15-64 Ph Me H H H H H H Ph H H H H 15-65 Ph Me H H H H H H H Ph H H H 15-66 Ph Me H H H H H H H H Ph H H 15-67 Ph Me H H H H H H H H H Ph H 15-68 Ph Me H H H H H H H H H H Ph
15-69 Me H Me H H H H H H H H H H 15-70 Me H Me H H Me H H H H H H H 15-71 Me H Me H H H Me H H H H H H 15-72 Me H Me H H H H Me H H H H H 15-73 Me H Me H H H H H Me H H H H 15-74 Me H Me H H H H H H Me H H H 15-75 Me H Me H H H H H H H Me H H 15-76 Me H Me H H H H H H H H Me H 15-77 Me H Me H H H H H H H H H Me 15-78 Me H Me H H Ph H H H H H H H 15-79 Me H Me H H H Ph H H H H H H 15-80 Me H Me H H H H Ph H H H H H 15-81 Me H Me H H H H H Ph H H H H 15-82 Me H Me H H H H H H Ph H H H 15-83 Me H Me H H H H H H H Ph H H 15-84 Me H Me H H H H H H H H Ph H 15-85 Me H Me H H H H H H H H H Ph 15-86 Ph H Me H H H H H H H H H H 15-87 Ph H Me H H Me H H H H H H H 15-88 Ph H Me H H H Me H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 15- 89 Ph H Me H H H H Me H H H H H 15- 90 Ph H Me H H H H H Me H H H H 15- 91 Ph H Me H H H H H H Me H H H 15- 92 Ph H Me H H H H H H H Me H H 15- 93 Ph H Me H H H H H H H H Me H 15- 94 Ph H Me H H H H H H H H H Me 15- 95 Ph H Me H H Ph H H H H H H H 15- 96 Ph H Me H H H Ph H H H H H H 15- 97 Ph H Me H H H H Ph H H H H H 15- 98 Ph H Me H H H H H Ph H H H H 15- 99 Ph H Me H H H H H H Ph H H H 15- 100 Ph H Me H H H H H H H Ph H H 15- 101 Ph H Me H H H H H H H H Ph H 15- 102 Ph H Me H H H H H H H H H Ph
15- 103 Me H H Me H H H H H H H H H 15- 104 Me H H Me H Me H H H H H H H 15- 105 Me H H Me H H Me H H H H H H 15- 106 Me H H Me H H H Me H H H H H 15- 107 Me H H Me H H H H Me H H H H 15- 108 Me H H Me H H H H H Me H H H 15- 109 Me H H Me H H H H H H Me H H 15- 110 Me H H Me H H H H H H H Me H 15- 111 Me H H Me H H H H H H H H Me 15- 112 Me H H Me H Ph H H H H H H H 15- 113 Me H H Me H H Ph H H H H H H 15- 114 Me H H Me H H H Ph H H H H H 15- 115 Me H H Me H H H H Ph H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 15- 116 Me H H Me H H H H H Ph H H H 15- 117 Me H H Me H H H H H H Ph H H 15- 118 Me H H Me H H H H H H H Ph H 15- 119 Me H H Me H H H H H H H H Ph 15- 120 Ph H H Me H H H H H H H H H 15- 121 Ph H H Me H Me H H H H H H H 15- 122 Ph H H Me H H Me H H H H H H 15- 123 Ph H H Me H H H Me H H H H H 15- 124 Ph H H Me H H H H Me H H H H 15- 125 Ph H H Me H H H H H Me H H H 15- 126 Ph H H Me H H H H H H Me H H 15- 127 Ph H H Me H H H H H H H Me H 15- 128 Ph H H Me H H H H H H H H Me 15- 129 Ph H H Me H Ph H H H H H H H 15- 130 Ph H H Me H H Ph H H H H H H 15- 131 Ph - H H Me H H H Ph H H H H H 15- 132 Ph H H Me H H H H Ph H H H H 15- 133 Ph H H Me H H H H H Ph H H H 15- 134 Ph H H Me H H H H H H Ph H H 15- 135 Ph H H Me H H H H H H H Ph H 15- 136 Ph H H Me H H H H H H H H Ph
15- 137 Me H H H Me H H H H H H H H 15- 138 Me H H H Me Me H H H H H H H 15- 139 Me H H H Me H Me H H H H H H 15- 140 Me H H H Me H H Me H H H H H 15- 141 Me H H H Me H H H Me H H H H 15- 142 Me H H H Me H H H H Me H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 15- 143 Me H H H Me H H H H H Me H H 15- 144 Me H H H Me H H H H H H Me H 15- 145 Me H H H Me H H H H H H H Me 15- 146 Me H H H Me Ph H H H H H H H 15- 147 Me H H H Me H Ph H H H H H H 15- 148 Me H H H Me H H Ph H H H H H 15- 149 Me H H H Me H H H Ph H H H H 15- 150 Me H H H Me H H H H Ph H H H 15- 151 Me H H H Me H H H H H Ph H H 15- 152 Me H H H Me H H H H H H Ph H 15- 153 Me H H H Me H H H H H H H Ph 15- 154 Ph H H H Me H H H H H H H H 15- 155 Ph H H H Me Me H H H H H H H 15- 156 Ph H H H Me H Me H H H H H H 15- 157 Ph H H H Me H H Me H H H H H 15- 158 Ph H H H Me H H H Me H H H H 15- 159 Ph H H H Me H H H H Me H H H 15- 160 Ph H H H Me H H H H H Me H H 15- 161 Ph H H H Me H H H H H H Me H 15- 162 Ph H H H Me H H H H H H H Me 15- 163 Ph H H H Me Ph H H H H H H H 15- 164 Ph H H H Me H Ph H H H H H H 15- 165 Ph H H H Me H H Ph H H H H H 15- 166 Ph H H H Me H H H Ph H H H H 15- 167 Ph H H H Me H H H H Ph H H H 15- 168 Ph H H H Me H H H H H Ph H H 15- 169 Ph H H H Me H H H H H H Ph H 15- 170 Ph H H H Me H H H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8
15- 171 Me Ph H H H H H H H H H H H 15- 172 Me Ph H H H Me H H H H H H H 15- 173 Me Ph H H H H Me H H H H H H 15- 174 Me Ph H H H H H Me H H H H H 15- 175 Me Ph H H H H H H Me H H H H 15- 176 Me Ph H H H H H H H Me H H H 15- 177 Me Ph H H H H H H H H Me H H 15- 178 Me Ph H H H H H H H H H Me H 15- 179 Me Ph H H H H H H H H H H Me 15- 180 Me Ph H H H Ph H H H H H H H 15- 181 Me Ph H H H H Ph H H H H H H 15- 182 Me Ph H H H H H Ph H H H H H 15- 183 Me Ph H H H H H H Ph H H H H 15- 184 Me Ph H H H H H H H Ph H H H 15- 185 Me Ph H H H H H H H H Ph H H 15- 186 Me Ph H H H H H H H H H Ph H 15- 187 Me Ph H H H H H H H H H H Ph 15- 188 Ph Ph H H H H H H H H H H H 15- 189 Ph Ph H H H Me H H H H H H H 15- 190 Ph Ph H H H H Me H H H H H H 15- 191 Ph Ph H H H H H Me H H H H H 15- 192 Ph Ph H H H H H H Me H H H H 15- 193 Ph Ph H H H H H H H Me H H H 15- 194 Ph Ph H H H H H H H H Me H H 15- 195 Ph Ph H H H H H H H H H Me H 15- 196 Ph Ph H H H H H H H H H H Me 15- 197 Ph Ph H H H Ph H H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 15- 198 Ph Ph H H H H Ph H H H H H H 15- 199 Ph Ph H H H H H Ph H H H H H 15- 200 Ph Ph H H H H H H Ph H H H H 15- 201 Ph Ph H H H H H H H Ph H H H 15- 202 Ph Ph H H H H H H H H Ph H H 15- 203 Ph Ph H H H H H H H H H Ph H 15- 204 Ph Ph H H H H H H H H H H Ph
15- 205 Me H Ph H H H H H H H H H H 15- 206 Me H Ph H H Me H H H H H H H 15- 207 Me H Ph H H H Me H H H H H H 15- 208 Me H Ph H H H H Me H H H H H 15- 209 Me H Ph H H H H H Me H H H H 15- 210 Me H Ph H H H H H H Me H H H 15- 211 Me H Ph H H H H H H H Me H H 15- 212 Me H Ph H H H H H H H H Me H 15- 213 Me H Ph H H H H H H H H H Me 15- 214 Me H Ph H H Ph H H H H H H H 15- 215 Me H Ph H H H Ph H H H H H H 15- 216 Me H Ph H H H H Ph H H H H H 15- 217 Me H Ph H H H H H Ph H H H H 15- 218 Me H Ph H H H H H H Ph H H H 15- 219 Me H Ph H H H H H H H Ph H H 15- 220 Me H Ph H H H H H H H H Ph H 15- 221 Me H Ph H H H H H H H H H Ph 15- 222 Ph H Ph H H H H H H H H H H 15- 223 Ph H Ph H H Me H H H H H H H 15- 224 Ph H Ph H H H Me H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 15- 225 Ph H Ph H H H H Me H H H H H 15- 226 Ph H Ph H H H H H Me H H H H 15- 227 Ph H Ph H H H H H H Me H H H 15- 228 Ph H Ph H H H H H H H Me H H 15- 229 Ph H Ph H H H H H H H H Me H 15- 230 Ph H Ph H H H H H H H H H Me 15- 231 Ph H Ph H H Ph H H H H H H H 15- 232 Ph H Ph H H H Ph H H H H H H 15- 233 Ph H Ph H H H H Ph H H H H H 15- 234 Ph H Ph H H H H H Ph H H H H 15- 235 Ph H Ph H H H H H H Ph H H H 15- 236 Ph H Ph H H H H H H H Ph H H 15- 237 Ph H Ph H H H H H H H H Ph H 15- 238 Ph H Ph H H H H H H H H H Ph
15- 239 Me H H Ph H H H H H H H H H 15- 240 Me H H Ph H Me H H H H H H H 15- 241 Me H H Ph H H Me H H H H H H 15- 242 Me H H Ph H H H Me H H H H H 15- 243 Me H H Ph H H H H Me H H H H 15- 244 Me H H Ph H H H H H Me H H H 15- 245 Me H H Ph H H H H H H Me H H 15- 246 Me H H Ph H H H H H H H Me H 15- 247 Me H H Ph H H H H H H H H Me 15- 248 Me H H Ph H Ph H H H H H H H 15- 249 Me H H Ph H H Ph H H H H H H 15- 250 Me H H Ph H H H Ph H H H H H 15- 251 Me H H Ph H H H H Ph H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 15- 252 Me H H Ph H H H H H Ph H H H 15- 253 Me H H Ph H H H H H H Ph H H 15- 254 Me H H Ph H H H H H H H Ph H 15- 255 Me H H Ph H H H H H H H H Ph 15- 256 Ph H H Ph H H H H H H H H H 15- 257 Ph H H Ph H Me H H H H H H H 15- 258 Ph H H Ph H H Me H H H H H H 15- 259 Ph H H Ph H H H Me H H H H H 15- 260 Ph H H Ph H H H H Me H H H H 15- 261 Ph H H Ph H H H H H Me H H H 15- 262 Ph H H Ph H H H H H H Me H H 15- 263 Ph H H Ph H H H H H H H Me H 15- 264 Ph H H Ph H H H H H H H H Me 15- 265 Ph H H Ph H Ph H H H H H H H 15- 266 Ph H H Ph H H Ph H H H H H H 15- 267 Ph H H Ph H H H Ph H H H H H 15- 268 Ph H H Ph H H H H Ph H H H H 15- 269 Ph H H Ph H H H H H Ph H H H 15- 270 Ph H H Ph H H H H H H Ph H H 15- 271 Ph H H Ph H H H H H H H Ph H 15- 272 Ph H H Ph H H H H H H H H Ph
15- 273 Me H H H Ph H H H H H H H H 15- 274 Me H H H Ph Me H H H H H H H 15- 275 Me H H H Ph H Me H H H H H H 15- 276 Me H H H Ph H H Me H H H H H 15- 277 Me H H H Ph H H H Me H H H H 15- 278 Me H H H Ph H H H H Me H H H
Figure imgf000223_0001
Table 16
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 16-1 Me H H H H H H H H 16-2 Me H H H H H H Me H 16-3 Me H H H H H H H Me 16-4 Me H H H H H H Ph H 16-5 Me H H H H H H H Ph 16-6 Ph H H H H H H H H 16-7 Ph H H H H H H Me H 16-8 Ph H H H H H H H Me 16-9 Ph H H H H H H Ph H 16-10 Ph H H H H H H H Ph
16- 11 Me Me H H H H H H H 16-12 Me Me H H H H H Me H 16- 13 Me Me H H H H H H Me 16- 14 Me Me H H H H H Ph H 16- 15 Me Me H H H H H H Ph 16-16 Ph Me H H H H H H H 16-17 Ph Me H H H H H Me H 16-18 Ph Me H H H H H H Me 16-19 Ph Me H H H H H Ph H 16-20 Ph Me H H H H H H Ph
16-21 Me H Me H H H H H H 16-22 Me H Me H H H H Me H 16-23 Me H Me H H H H H Me 16-24 Me H Me H H H H Ph H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 16-25 Me H Me H H H H H Ph 16-26 Ph H Me H H H H H H 16-27 Ph H Me H H H H Me H 16-28 Ph H Me H H H H H Me 16-29 Ph H Me H H H H Ph H 16-30 Ph H Me H H H H H Ph
16-31 Me H H Me H H H H H 16-32 Me H H Me H H H Me H 16-33 Me H H Me H H H H Me 16-34 Me H H Me H H H Ph H 16-35 Me H H Me H H H H Ph 16-36 Ph H H Me H H H H H 16-37 Ph H H Me H H H Me H 16-38 Ph H H Me H H H H Me 16-39 Ph H H Me H H H Ph H 16-40 Ph H H Me H H H H Ph
16-41 Me H H H Me H H H H 16-42 Me H H H Me H H Me H 16-43 Me H H H Me H H H Me 16-44 Me H H H Me H H Ph H 16-45 Me H H H Me H H H Ph 16-46 Ph H H H Me H H H H 16-47 Ph H H H Me H H Me H 16-48 Ph H H H Me H H H Me 16-49 Ph H H H Me H H Ph H 16-50 Ph H H H Me H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2
16-51 Me H H H H Me H H H 16-52 Me H H H H Me H Me H 16-53 Me H H H H Me H H Me 16-54 Me H H H H Me H Ph H 16-55 Me H H H H Me H H Ph 16-56 Ph H H H H Me H H H 16-57 Ph H H H H Me H Me H 16-58 Ph H H H H Me H H Me 16-59 Ph H H H H Me H Ph H 16-60 Ph H H H H Me H H Ph
16-61 Me H H H H H Me H H 16-62 Me H H H H H Me Me H 16-63 Me H H H H H Me H Me 16-64 Me H H H H H Me Ph H 16-65 Me H H H H H Me H Ph 16-66 Ph H H H H H Me H H 16-67 Ph H H H H H Me Me H 16-68 Ph H H H H H Me H Me 16-69 Ph H H H H H Me Ph H 16-70 Ph H H H H H Me H Ph
16-71 Me Ph H H H H H H H 16-72 Me Ph H H H H H Me H 16-73 Me Ph H H H H H H Me 16-74 Me Ph H H H H H Ph H 16-75 Me Ph H H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 16-76 Ph Ph H H H H H H H 16-77 Ph Ph H H H H H Me H 16-78 Ph Ph H H H H H H Me 16-79 Ph Ph H H H H H Ph H 16-80 Ph Ph H H H H H H Ph
16-81 Me H Ph H H H H H H 16-82 Me H Ph H H H H Me H 16-83 Me H Ph H H H H H Me 16-84 Me H Ph H H H H Ph H 16-85 Me H Ph H H H H H Ph 16-86 Ph H Ph H H H H H H 16-87 Ph H Ph H H H H Me H 16-88 Ph H Ph H H H H H Me 16-89 Ph H Ph H H H H Ph H 16-90 Ph H Ph H H H H H Ph
16-91 Me H H Ph H H H H H 16-92 Me H H Ph H H H Me H 16-93 Me H H Ph H H H H Me 16-94 Me H H Ph H H H Ph H 16-95 Me H H Ph H H H H Ph 16-96 Ph H H Ph H H H H H 16-97 Ph H H Ph H H H Me H 16-98 Ph H H Ph H H H H Me 16-99 Ph H H Ph H H H Ph H 16- 100 Ph H H Ph H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 16- 101 Me H H H Ph H H H H 16- 102 Me H H H Ph H H Me H 16- 103 Me H H H Ph H H H Me 16- 104 Me H H H Ph H H Ph H 16- 105 Me H H H Ph H H H Ph 16- 106 Ph H H H Ph H H H H 16- 107 Ph H H H Ph H H Me H 16- 108 Ph H H H Ph H H H Me 16- 109 Ph H H H Ph H H Ph H 16- 110 Ph H H H Ph H H H Ph
16- 111 Me H H H H Ph H H H 16- 112 Me H H H H Ph H Me H 16- 113 Me H H H H Ph H H Me 16- 114 Me H H H H Ph H Ph H 16- 115 Me H H H H Ph H H Ph 16- 116 Ph H H H H Ph H H H 16- 117 Ph H H H H Ph H Me H 16- 118 Ph H H H H Ph H H Me 16- 119 Ph H H H H Ph H Ph H 16- 120 Ph H H H H Ph H H Ph
16- 121 Me H H H H H Ph H H 16- 122 Me H H H H H Ph Me H 16- 123 Me H H H H H Ph H Me 16- 124 Me H H H H H Ph Ph H 16- 125 Me H H H H H Ph H Ph 16- 126 Ph H H H H H Ph H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 16- 127 Ph H H H H H Ph Me H 16- 128 Ph H H H H H Ph H Me 16- 129 Ph H H H H H Ph Ph H 16- 130 Ph H H H H H Ph H Ph
Table 17
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 17-1 Me H H H H H H H H H H 17-2 Me H H H H H H Me H H H 17-3 Me H H H H H H H Me H H 17-4 Me H H H H H H H H Me H 17-5 Me H H H H H H H H H Me 17-6 Me H H H H H H Ph H H H 17-7 Me H H H H H H H Ph H H 17-8 Me H H H H H H H H Ph H 17-9 Me H H H H H H H H H Ph 17-10 Ph H H H H H H H H H H 17-11 Ph H H H H H H Me H H H 17- 12 Ph H H H H H H H Me H H 17-13 Ph H H H H H H H H Me H 17-14 Ph H H H H H H H H H Me 17-15 Ph H H H H H H Ph H H H 17-16 Ph H H H H H H H Ph H H 17- 17 Ph H H H H H H H H Ph H 17- 18 Ph H H H H H H H H H Ph
17- 19 Me Me H H H H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 17-20 Me Me H H H H H Me H H H 17-21 Me Me H H H H H H Me H H 17-22 Me Me H H H H H H H Me H 17-23 Me Me H H H H H H H H Me 17-24 Me Me H H H H H Ph H H H 17-25 Me Me H H H H H H Ph H H 17-26 Me Me H H H H H H H Ph H 17-27 Me Me H H H H H H H H Ph 17-28 Ph Me H H H H H H H H H 17-29 Ph Me H H H H H Me H H H 17-30 Ph Me H H H H H H Me H H 17-31 Ph Me H H H H H H H Me H 17-32 Ph Me H H H H H H H H Me 17-33 Ph Me H H H H H Ph H H H 17-34 Ph Me H H H H H H Ph H H 17-35 Ph Me H H H H H H H Ph H 17-36 Ph Me H H H H H H H H Ph
17-37 Me H Me H H H H 17-38 Me H Me H H H H Me H H H 17-39 Me H Me H H H H H Me H H 17-40 Me H Me H H H H H H Me H 17-41 Me H Me H H H H H H H Me 17-42 Me H Me H H H H Ph H H H 17-43 Me H Me H H H H H Ph H H 17-44 Me H Me H H H H H H Ph H 17-45 Me H Me H H H H H H H Ph 17-46 Ph H Me H H H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 17-47 Ph H Me H H H H Me H H H 17-48 Ph H Me H H H H H Me H H 17-49 Ph H Me H H H H H H Me H 17-50 Ph H Me H H H H H H H Me 17-51 Ph H Me H H H H Ph H H H 17-52 Ph H Me H H H H H Ph H H 17-53 Ph H Me H H H H H H Ph H 17-54 Ph H Me H H H H H H H Ph
17-55 Me H H Me H H H H H H H 17-56 Me H H Me H H H Me H H H 17-57 Me H H Me H H H H Me H H 17-58 Me H H Me H H H H H Me H 17-59 Me H H Me H H H H H H Me 17-60 Me H H Me H H H Ph H H H 17-61 Me H H Me H H H H Ph H H 17-62 Me H H Me H H H H H Ph H 17-63 Me H H Me H H H H H H Ph 17-64 Ph H H Me H H H H H H H 17-65 Ph H H Me H H H Me H H H 17-66 Ph H H Me H H H H Me H H 17-67 Ph H H Me H H H H H Me H 17-68 Ph H H Me H H H H H H Me 17-69 Ph H H Me H H H Ph H H H 17-70 Ph H H Me H H H H Ph H H 17-71 Ph H H Me H H H H H Ph H 17-72 Ph H H Me H H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 RaS Ra6 Ra7 Rbl Rb2 Rb3 Rb4 17-73 Me H H H Me H H H H H H 17-74 Me H H H Me H H Me H H H 17-75 Me H H H Me H H H Me H H 17-76 Me H H H Me H H H H Me H 17-77 Me H H H Me H H H H H Me 17-78 Me H H H Me H H Ph H H H 17-79 Me H H H Me H H H Ph H H 17-80 Me H H H Me H H H H Ph H 17-81 Me H H H Me H H H H H Ph 17-82 Ph H H H Me H H H H H H 17-83 Ph ' H H H Me H H Me H H H 17-84 Ph H H H Me H H H Me H H 17-85 Ph H H H Me H H H H Me H 17-86 Ph H H H Me H H H H H Me 17-87 Ph H H H Me H H Ph H H H 17-88 Ph H H H Me H H H Ph H H 17-89 Ph H H H Me H H H H Ph H 17-90 Ph H H H Me H H H H H Ph
17-91 Me H H H H Me H H H H H 17-92 Me H H H H Me H Me H H H 17-93 Me H H H H Me H H Me H H 17-94 Me H H H H Me H H H Me H 17-95 Me H H H H Me H H H H Me 17-96 Me H H H H Me H Ph H H H 17-97 Me H H H H Me H H Ph H H 17-98 Me H H H H Me H H H Ph H 17-99 Me H H H H Me H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 17- 100 Ph H H H H Me H H H H H 17- 101 Ph H H H H Me H Me H H H 17- 102 Ph H H H H Me H H Me H H 17- 103 Ph H H H H Me H H H Me H 17- 104 Ph H H H H Me H H H H Me 17- 105 Ph H H H H Me H Ph H H H 17- 106 Ph H H H H Me H H Ph H H 17- 107 Ph H H H H Me H H H Ph H 17- 108 Ph H H H H Me H H H H Ph
17- 109 Me H H H H H Me H H H H 17- 110 Me H H H H H Me Me H H H 17- 111 Me H H H H H Me H Me H H 17- 112 Me H H H H H Me H H Me H 17- 113 Me H H H H H Me H H H Me 17- 114 Me H H H H H Me Ph H H H 17- 115 Me H H H H H Me H Ph H H 17- 116 Me H H H H H Me H H Ph H 17- 117 Me H H H H H Me H H H Ph 17- 118 Ph H H H H H Me H H H H 17- 119 Ph H H H H H Me Me H H H 17- 120 Ph H H H H H Me H Me H H 17- 121 Ph H H H H H Me H H Me H 17- 122 Ph H H H H H Me H H H Me 17- 123 Ph H H H H H Me Ph H H H 17- 124 Ph H H H H H Me H Ph H H 17- 125 Ph H H H H H Me H H Ph H 17- 126 Ph H H H H H Me H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4
17- 127 Me Ph H H H H H H H H H 17- 128 Me Ph H H H H H Me H H H 17- 129 Me Ph H H H H H H Me H H 17- 130 Me Ph H H H H H H H Me H 17- 131 Me Ph H H H H H H H H Me 17- 132 Me Ph H H H H H Ph H H H 17- 133 Me Ph H H H H H H Ph H H 17- 134 Me Ph H H H H H H H Ph H 17- 135 Me Ph H H H H H H H H Ph 17- 136 Ph Ph H H H H H H H H H 17- 137 Ph Ph H H H H H Me H H H 17- 138 Ph Ph H H H H H H Me H H 17- 139 Ph Ph H H H H H H H Me H 17- 140 Ph Ph H H H H H H H H Me 17- 141 Ph Ph H H H H H Ph H H H 17- 142 Ph Ph H H H H H H Ph H H 17- 143 Ph Ph H H H H H H H Ph H 17- 144 Ph Ph H H H H H H H H Ph
17- 145 Me H Ph H H H H H H H H 17- 146 Me H Ph H H H H Me H H H 17- 147 Me H Ph H H H H H Me H H 17- 148 Me H Ph H H H H H H Me H 17- 149 Me H Ph H H H H H H H Me 17- 150 Me H Ph H H H H Ph H H H 17- 151 Me H Ph H H H H H Ph H H 17- 152 Me H Ph H H H H H H Ph H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 17- 153 Me H Ph H H H H H H H Ph 17- 154 Ph H Ph H H H H H H H H 17- 155 Ph H Ph H H H H Me H H H 17- 156 Ph H Ph H H H H H Me H H 17- 157 Ph H Ph H H H H H H Me H 17- 158 Ph H Ph H H H H H H H Me 17- 159 Ph H Ph H H H H Ph H H H 17- 160 Ph H Ph H H H H H Ph H H 17- 161 Ph H Ph H H H H H H Ph H 17- 162 Ph H Ph H H H H H H H Ph
17- 163 Me H H Ph H H H H H H H 17- 164 Me H H Ph H H H Me H H H 17- 165 Me H H Ph H H H H Me H H 17- 166 Me H H Ph H H H H H Me H 17- 167 Me H H Ph H H H H H H Me 17- 168 Me H H Ph H H H Ph H H H 17- 169 Me H H Ph H H H H Ph H H 17- 170 Me H H Ph H H H H H Ph H 17- 171 Me H H Ph H H H H H H Ph 17- 172 Ph H H Ph H H H H H H H 17- 173 Ph H H Ph H H H Me H H H 17- 174 Ph H H Ph H H H H Me H H 17- 175 Ph H H Ph H H H H H Me H 17- 176 Ph H H Ph H H H H H H Me 17- 177 Ph H H Ph H H H Ph H H H 17- 178 Ph H H Ph H H H H Ph H H 17- 179 Ph H H Ph H H H H H Ph H
Figure imgf000236_0001
- 181 Me H H H Ph H H H H H H - 182 Me H H H Ph H H Me H H H - 183 Me H H H Ph H H H Me H H - 184 Me H H H Ph H H H H Me H - 185 Me H H H Ph H H H H H Me - 186 Me H H H Ph H H Ph H H H - 187 Me H H H Ph H H H Ph H H - 188 Me H H H Ph H H H H Ph H - 189 Me H H H Ph H H H H H Ph - 190 Ph H H H Ph H H H H H H - 191 Ph H H H Ph H H Me H H H - 192 Ph H H H Ph H H H Me H H - 193 Ph H H H Ph H H H H Me H - 194 Ph H H H Ph H H H H H Me - 195 Ph H H H Ph H H Ph H H H - 196 Ph H H H Ph H H H Ph H H - 197 Ph H H H Ph H H H H Ph H - 198 Ph H H H Ph H H H H H Ph - 199 Me H H H H Ph H H H H H - 200 Me H H H H Ph H Me H H H - 201 Me H H H H Ph H H Me H H - 202 Me H H H H Ph H H H Me H - 203 Me H H H H Ph H H H H Me - 204 Me H H H H Ph H Ph H H H - 205 Me H H H H Ph H H Ph H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 17- 206 Me H H H H Ph H H H Ph H 17- 207 Me H H H H Ph H H H H Ph 17- 208 Ph H H H H Ph H H H H H 17- 209 Ph H H H H Ph H Me H H H 17- 210 Ph H H H H Ph H H Me H H 17- 211 Ph H H H H Ph H H H Me H 17- 212 Ph H H H H Ph H H H H Me 17- 213 Ph H H H H Ph H Ph H H H 17- 214 Ph H H H H Ph H H Ph H H 17- 215 Ph H H H H Ph H H H Ph H 17- 216 Ph H H H H Ph H H H H Ph
17- 217 Me H H H H H Ph H H H H 17- 218 Me H H H H H Ph Me H H H 17- 219 Me H H H H H Ph H Me H H 17- 220 Me H H H H H Ph H H Me H 17- 221 Me H H H H H Ph H H H Me 17- 222 Me H H H H H Ph Ph H H H 17- 223 Me H H H H H Ph H Ph H H 17- 224 Me H H H H H Ph H H Ph H 17- 225 Me H H H H H Ph H H H Ph 17- 226 Ph H H H H H Ph H H H H 17- 227 Ph H H H H H Ph Me H H H 17- 228 Ph H H H H H Ph H Me H H 17- 229 Ph H H H H H Ph H H Me H 17- 230 Ph H H H H H Ph H H H Me 17- 231 Ph H H H H H Ph Ph H H H 17- 232 Ph H H H H H Ph H Ph H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 17- 233 Ph H H H H H Ph H H Ph H 17- 234 Ph H H H H H Ph H H H Ph
Table 18
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 18- 1 Me H H H H H H H H H H H H 18-2 Me H H H H H H Me H H H H H 18-3 Me H H H H H H H Me H H H H 18-4 Me H H H H H H H H Me H H H 18-5 Me H H H H H H H H H Me H H 18-6 Me H H H H H H H H H H Me H 18-7 Me H H H H H H H H H H H Me 18-8 Me H H H H H H Ph H H H H H 18-9 Me H H H H H H H Ph H H H H 18-10 Me H H H H H H H H Ph H H H 18-11 Me H H H H H H H H H Ph H H 18- 12 Me H H H H H H H H H H Ph H 18- 13 Me H H H H H H H H H H H Ph 18-14 Ph H H H H H H H H H H H H 18-15 Ph H H H H H H Me H H H H H 18- 16 Ph H H H H H H H Me H H H H 18-17 Ph H H H H H H H H Me H H H 18- 18 Ph H H H H H H H H H Me H H 18-19 Ph H H H H H H H H H H Me H 18-20 Ph H H H H H H H H H H H Me 18-21 Ph H H H H H H Ph H H H H H 18-22 Ph H H H H H H H Ph H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 18-23 Ph H H H H H H H H Ph H H H 18-24 Ph H H H H H H H H H Ph H H 18-25 Ph H H H H H H H H H H Ph H 18-26 Ph H H H H H H H H H H H Ph
18-27 Me Me H H H H H H H H H H H 18-28 Me Me H H H H H Me H H H H H 18-29 Me Me H H H H H H Me H H H H 18-30 Me Me H H H H H H H Me H H H 18-31 Me Me H H H H H H H H Me H H 18-32 Me Me H H H H H H H H H Me H 18-33 Me Me H H H H H H H H H H Me 18-34 Me Me H H H H H Ph H H H H H 18-35 Me Me H H H H H H Ph H H H H 18-36 Me Me H H H H H H H Ph H H H 18-37 Me Me H H H H H H H H Ph H H 18-38 Me Me H H H H H H H H H Ph H 18-39 Me Me H H H H H H H H H H Ph 18-40 Ph Me H H H H H H H H H H H 18-41 Ph Me H H H H H Me H H H H H 18-42 Ph Me H H H H H H Me H H H H 18-43 Ph Me H H H H H H H Me H H H 18-44 Ph Me H H H H H H H H Me H H 18-45 Ph Me H H H H H H H H H Me H 18-46 Ph Me H H H H H H H H H H Me 18-47 Ph Me H H H H H Ph H H H H H 18-48 Ph Me H H H H H H Ph H H H H 18-49 Ph Me H H H H H H H Ph H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 18- 50 Ph Me H H H H H H H H Ph H H 18- 51 Ph Me H H H H H H H H H Ph H 18- 52 Ph Me H H H H H H H H H H Ph
18-53 Me H Me H H H H H H H H H H 18-54 Me H Me H H H H Me H H H H H 18-55 Me H Me H H H H H Me H H H H 18-56 Me H Me H H H H H H Me H H H 18-57 Me H Me H H H H H H H Me H H 18-58 Me H Me H H H H H H H H Me H 18-59 Me H Me H H H H H H H H H Me 18-60 Me H Me H H H H Ph H H H H H 18-61 Me H Me H H H H H Ph H H H H 18-62 Me H Me H H H H H H Ph H H H 18-63 Me H Me H H H H H H H Ph H H 18-64 Me H Me H H H H H H H H Ph H 18-65 Me H Me H H H H H H H H H Ph 18-66 Ph H Me H H H H H H H H H H 18-67 Ph H Me H H H H Me H H H H H 18-68 Ph H Me H H H H H Me H H H H 18-69 Ph H Me H H H H H H Me H H H 18-70 Ph H Me H H H H H H H Me H H 18-71 Ph H Me H H H H H H H H Me H 18-72 Ph H Me H H H H H H H H H Me 18-73 Ph H Me H H H H Ph H H H H H 18-74 Ph H Me H H H H H Ph H H H H 18-75 Ph H Me H H H H H H Ph H H H 18-76 Ph H Me H H H H H H H Ph H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 RbS Rb6 18-77 Ph H Me H H H H H H H H Ph H 18-78 Ph H Me H H H H H H H H H Ph
18-79 Me H H Me H H H H H H H H H 18-80 Me H H Me H H H Me H H H H H 18-81 Me H H Me H H H H Me H H H H 18-82 Me H H Me H H H H H Me H H H 18-83 Me H H Me H H H H H H Me H H 18-84 Me H H Me H H H H H H H Me H 18-85 Me H H Me H H H H H H H H Me 18-86 Me H H Me H H H Ph H H H H H 18-87 Me H H Me H H H H Ph H H H H 18-88 Me H H Me H H H H H Ph H H H 18-89 Me H H Me H H H H H H Ph H H 18-90 Me H H Me H H H H H H H Ph H 18-91 Me H H Me H H H H H H H H Ph 18-92 Ph H H Me H H H H H H H H H 18-93 Ph H H Me H H H Me H H H H H 18-94 Ph H H Me H H H H Me H H H H 18-95 Ph H H Me H H H H H Me H H H 18-96 Ph H H Me H H H H H H Me H H 18-97 Ph H H Me H H H H H H H Me H 18-98 Ph H H Me H H H H H H H H Me 18-99 Ph H H Me H H H Ph H H H H H 18- 100 Ph H H Me H H H H Ph H H H H 18-101 Ph H H Me H H H H H Ph H H H 18- 102 Ph H H Me H H H H H H Ph H H 18- 103 Ph H H Me H H H H H H H Ph H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 18- 104 Ph H H Me H H H H H H H H Ph
18- 105 Me H H H Me H H H H H H H H 18- 106 Me H H H Me H H Me H H H H H 18- 107 Me H H H Me H H H Me H H H H 18- 108 Me H H H Me H H H H Me H H H 18- 109 Me H H H Me H H H H H Me H H 18- 110 Me H H H Me H H H H H H Me H 18- 111 Me H H H Me H H H H H H H Me 18- 112 Me H H H Me H H Ph H H H H H 18- 113 Me H H H Me H H H Ph H H H H 18- 114 Me H H H Me H H H H Ph H H H 18- 115 Me H H H Me H H H H H Ph H H 18- 116 Me H H H Me H H H H H H Ph H 18- 117 Me H H H Me H H H H H H H Ph 18- 118 Ph H H H Me H H H H H H H H 18- 119 Ph H H H Me H H Me H H H H H 18- 120 Ph H H H Me H H H Me H H H H 18- 121 Ph H H H Me H H H H Me H H H 18- 122 Ph H H H Me H H H H H Me H H 18- 123 Ph H H H Me H H H H H H Me H 18- 124 Ph H H H Me H H H H H H H Me 18- 125 Ph H H H Me H H Ph H H H H H 18- 126 Ph H H H Me H H H Ph H H H H 18- 127 Ph H H H Me H H H H Ph H H H 18- 128 Ph H H H Me H H H H H Ph H H 18- 129 Ph H H H Me H H H H H H Ph H 18- 130 Ph H H H Me H H H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6
18- 131 Me H H H H Me H H H H H H H 18- 132 Me H H H H Me H Me H H H H H 18- 133 Me H H H H Me H H Me H H H H 18- 134 Me H H H H Me H H H Me H H H 18- 135 Me H H H H Me H H H H Me H H 18- 136 Me H H H H Me H H H H H Me H 18- 137 Me H H H H Me H H H H H H Me 18- 138 Me H H H H Me H Ph H H H H H 18- 139 Me H H H H Me H H Ph H H H H 18- 140 Me H H H H Me H H H Ph H H H 18- 141 Me H H H H Me H H H H Ph H H 18- 142 Me H H H H Me H H H H H Ph H 18- 143 Me H H H H Me H H H H H H Ph 18- 144 Ph H H H H Me H H H H H H H 18- 145 Ph H H H H Me H Me H H H H H 18- 146 Ph H H H H Me H H Me H H H H 18- 147 Ph H H H H Me H H H Me H H H 18- 148 Ph H H H H Me H H H H Me H H 18- 149 Ph H H H H Me H H H H H Me H 18- 150 Ph H H H H Me H H H H H H Me 18- 151 Ph H H H H Me H Ph H H H H H 18- 152 Ph H H H H Me H H Ph H H H H 18- 153 Ph H H H H Me H H H Ph H H H 18- 154 Ph H H H H Me H H H H Ph H H 18- 155 Ph H H H H Me H H H H H Ph H 18- 156 Ph H H H H Me H H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 18- 157 Me H H H H H Me H H H H H H 18- 158 Me H H H H H Me Me H H H H H 18- 159 Me H H H H H Me H Me H H H H 18- 160 Me H H H H H Me H H Me H H H 18- 161 Me H H H H H Me H H H Me H H 18- 162 Me H H H H H Me H H H H Me H 18- 163 Me H H H H H Me H H H H H Me 18- 164 Me H H H H H Me Ph H H H H H 18- 165 Me H H H H H Me H Ph H H H H 18- 166 Me H H H H H Me H H Ph H H H 18- 167 Me H H H H H Me H H H Ph H H 18- 168 Me H H H H H Me H H H H Ph H 18- 169 Me H H H H H Me H H H H H Ph 18- 170 Ph H H H H H Me H H H H H H 18- 171 Ph H H H H H Me Me H H H H H 18- 172 Ph H H H H H Me H Me H H H H 18- 173 Ph H H H H H Me H H Me H H H 18- 174 Ph H H H H H Me H H H Me H H 18- 175 Ph H H H H H Me H H H H Me H 18- 176 Ph H H H H H Me H H H H H Me 18- 177 Ph H H H H H Me Ph H H H H H 18- 178 Ph H H H H H Me H Ph H H H H 18- 179 Ph H H H H H Me H H Ph H H H 18- 180 Ph H H H H H Me H H H Ph H H 18- 181 Ph H H H H H Me H H H H Ph H 18- 182 Ph H H H H H Me H H H H H Ph
18- 183 Me Ph H H H H H H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 8- 184 Me Ph H H H H H Me H H H H H 8- 185 Me Ph H H H H H H Me H H H H 8- 186 Me Ph H H H H H H H Me H H H 8- 187 Me Ph H H H H H H H H Me H H 8- 188 Me Ph H H H H H H H H H Me H 8- 189 Me Ph H H H H H H H H H H Me 8- 190 Me Ph H H H H H Ph H H H H H 8- 191 Me Ph H H H H H H Ph H H H H 8- 192 Me Ph H H H H H H H Ph H H H 8- 193 Me Ph H H H H H H H H Ph H H 8- 194 Me Ph H H H H H H H H H Ph H 8- 195 Me Ph H H H H H H H H H H Ph 8- 196 Ph Ph H H H H H H H H H H H 8- 197 Ph Ph H H H H H Me H H H H H 8- 198 Ph Ph H H H H H H Me H H H H - 199 Ph Ph H H H H H H H Me H H H - 200 Ph Ph H H H H H H H H Me H H - 201 Ph Ph H H H H H H H H H Me H - 202 Ph Ph H H H H H H H H H H Me - 203 Ph Ph H H H H H Ph H H H H H - 204 Ph Ph H H H H H H Ph H H H H ,- 205 Ph Ph H H H H H H H Ph H H H :- 206 Ph Ph H H H H H H H H Ph H H :- 207 Ph Ph H H H H H H H H H Ph H ;- 208 Ph Ph H H H H H H H H H H Ph
209 Me H Ph H H H H H H H H H H 210 Me H Ph H H H H Me H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 18-211 Me H Ph H H H H H Me H H H H 18-212 Me H Ph H H H H H H Me H H H 18-213 Me H Ph H H H H H H H Me H H 18-214 Me H Ph H H H H H H H H Me H 18-215 Me H Ph H H H H H H H H H Me 18-216 Me H Ph H H H H Ph H H H H H 18-217 Me H Ph H H H H H Ph H H H H 18-218 Me H Ph H H H H H H Ph H H H 18-219 Me H Ph H H H H H H H Ph H H 18-220 Me H Ph H H H H H H H H Ph H 18-221 Me H Ph H H H H H H H H H Ph 18-222 Ph H Ph H H H H H H H H H H 18-223 Ph H Ph H H H H Me H H H H H 18-224 Ph H Ph H H H H H Me H H H H 18-225 Ph H Ph H H H H H H Me H H H 18-226 Ph H Ph H H H H H H H Me H H 18-227 Ph H Ph H H H H H H H H Me H 18-228 Ph H Ph H H H H H H H H H Me 18-229 Ph H Ph H H H H Ph H H H H H 18-230 Ph H Ph H H H H H Ph H H H H 18-231 Ph H Ph H H H H H H Ph H H H 18- 232 Ph H Ph H H H H H H H Ph H H 18- 233 Ph H Ph H H H H H H H H Ph H 18-234 Ph H Ph H H H H H H H H H Ph
18- 235 Me H H Ph H H H H H H H H H 18-236 Me H H Ph H H H Me H H H H H 18-237 Me H H Ph H H H H Me H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 18- 238 Me H H Ph H H H H H Me H H H 18- 239 Me H H Ph H H H H H H Me H H 18- 240 Me H H Ph H H H H H H H Me H 18- 241 Me H H Ph H H H H H H H H Me 18- 242 Me H H Ph H H H Ph H H H H H 18- 243 Me H H Ph H H H H Ph H H H H 18- 244 Me H H Ph H H H H H Ph H H H 18- 245 Me H H Ph H H H H H H Ph H H 18- 246 Me H H Ph H H H H H H H Ph H 18- 247 Me H H Ph H H H H H H H H Ph 18- 248 Ph H H Ph H H H H H H H H H 18- 249 Ph H H Ph H H H Me H H H H H 18- 250 Ph H H Ph H H H H Me H H H H 18- 251 Ph H H Ph H H H H H Me H H H 18- 252 Ph H H Ph H H H H H H Me H H 18- 253 Ph H H Ph H H H H H H H Me H 18- 254 Ph H H Ph H H H H H H H H Me 18- 255 Ph H H Ph H H H Ph H H H H H 18- 256 Ph H H Ph H H H H Ph H H H H 18- 257 Ph H H Ph H H H H H Ph H H H 18- 258 Ph H H Ph H H H H H H Ph H H 18- 259 Ph H H Ph H H H H H H H Ph H 18- 260 Ph H H Ph H H H H H H H H Ph
18- 261 Me H H H Ph H H H H H H H H 18- 262 Me H H H Ph H H Me H H H H H 18- 263 Me H H H Ph H H H Me H H H H 18- 264 Me H H H Ph H H H H Me H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 18- 265 Me H H H Ph H H H H H Me H H 18- 266 Me H H H Ph H H H H H H Me H 18- 267 Me H H H Ph H H H H H H H Me 18- 268 Me H H H Ph H H Ph H H H H H 18- 269 Me H H H Ph H H H Ph H H H H 18- 270 Me H H H Ph H H H H Ph H H H 18- 271 Me H H H Ph H H H H H Ph H H 18- 272 Me H H H Ph H H H H H H Ph H 18- 273 Me H H H Ph H H H H H H H Ph 18- 274 Ph H H H Ph H H H H H H H H 18- 275 Ph H H H Ph H H Me H H H H H 18- 276 Ph H H H Ph H H H Me H H H H 18- 277 Ph H H H Ph H H H H Me H H H 18- 278 Ph H H H Ph H H H H H Me H H 18- 279 Ph H H H Ph H H H H H H Me H 18- 280 Ph H H H Ph H H H H H H H Me 18- 281 Ph H H H Ph H H Ph H H H H H 18- 282 Ph H H H Ph H H H Ph H H H H 18- 283 Ph H H H Ph H H H H Ph H H H 18- 284 Ph H H H Ph H H H H H Ph H H 18- 285 Ph H H H Ph H H H H H H Ph H 18- 286 Ph H H H Ph H H H H H H H Ph
18- 287 Me H H H H Ph H H H H H H H 18- 288 Me H H H H Ph H Me H H H H H 18- 289 Me H H ' H H Ph H H Me H H H H 18- 290 Me H H H H Ph H H H Me H H H 18- 291 Me H H H H Ph H H H H Me H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 18- 292 Me H H H H Ph H H H H H Me H 18- 293 Me H H H H Ph H H H H H H Me 18- 294 Me H H H H Ph H Ph H H H H H 18- 295 Me H H H H Ph H H Ph H H H H 18- 296 Me H H H H Ph H H H Ph H H H 18- 297 Me H H H H Ph H H H H Ph H H 18- 298 Me H H H H Ph H H H H H Ph H 18- 299 Me H H H H Ph H H H H H H Ph 18- 300 Ph H H H H Ph H H H H H H H 18- 301 Ph H H H H Ph H Me H H H H H 18- 302 Ph H H H H Ph H H Me H H H H 18- 303 Ph H H H H Ph H H H Me H H H 18- 304 Ph H H H H Ph H H H H Me H H 18- 305 Ph H H H H Ph H H H H H Me H 18- 306 Ph H H H H Ph H H H H H H Me 18- 307 Ph H H H H Ph H Ph H H H H H 18- 308 Ph H H H H Ph H H Ph H H H H 18- 309 Ph H H H H Ph H H H Ph H H H 18- 310 Ph H H H H Ph H H H H Ph H H 18- 311 Ph H H H H Ph H H H H H Ph H 18- 312 Ph H H H H Ph H H H H H H Ph
18- 313 Me H H H H H Ph H H H H H H 18- 314 Me H H H H H Ph Me H H H H H 18- 315 Me H H H H H Ph H Me H H H H 18- 316 Me H H H H H Ph H H Me H H H 18- 317 Me H H H H H Ph H H H Me H H 18- 318 Me H H H H H Ph H H H H Me H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 18- 319 Me H H H H H Ph H H H H H Me 18- 320 Me H H H H H Ph Ph H H H H H 18- 321 Me H H H H H Ph H Ph H H H H 18- 322 Me H H H H H Ph H H Ph H H H 18- 323 Me H H H H H Ph H H H Ph H H 18- 324 Me H H H H H Ph H H H H Ph H 18- 325 Me H H H H H Ph H H H H H Ph 18- 326 Ph H H H H H Ph H H H H H H 18- 327 Ph H H H H H Ph Me H H H H H 18- 328 Ph H H H H H Ph H Me H H H H 18- 329 Ph H H H H H Ph H H Me H H H 18- 330 Ph H H H H H Ph H H H Me H H 18- 331 Ph H H H H H Ph H H H H Me H 18- 332 Ph H H H H H Ph H H H H H Me 18- 333 Ph H H H H H Ph Ph H H H H H 18- 334 Ph H H H H H Ph H Ph H H H H 18- 335 Ph H H H H H Ph H H Ph H H H 18- 336 Ph H H H H H Ph H H H Ph H H 18- 337 Ph H H H H H Ph H H H H Ph H 18- 338 Ph H H H H H Ph H H H H H Ph
Table 19
Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 i Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 19-1 1 Me H H H H H H H H H H H H Me 19-1 2 Me H H H H H H Me H H H H H Me 19-1 3 Me H H H H H H H Me H H H H Me 19-1 4 Me H H H H H H H H Me H H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7
19-1 5 Me H H H H H H H H H Me H H Me
19-1 6 Me H H H H H H H H H H Me H Me
19-1 7 Me H H H H H H H H H H H Me Me
19-1 8 Me H H H H H H Ph H H H H H Me
19-1 9 Me H H H H H H H Ph H H H H Me
19-1 10 Me H H H H H H H H Ph H H H Me
19-1 11 Me H H H H H H H H H Ph H H Me
19-1 12 Me H H H H H H H H H H Ph H Me
19-1 13 Me H H H H H H H H H H H Ph Me
19-1 14 Ph H H H H H H H H H H H H Me
19-1 15 Ph H H H H H H Me H H H H H Me
19-1 16 Ph H H H H H H H Me H H H H Me
19-1 17 Ph H H H H H H H H Me H H H Me
19-1 18 Ph H H H H H H H H H Me H H Me
19-1 19 Ph H H H H H H H H H H Me H Me
19-1 20 Ph H H H H H H H H H H H Me Me
19-1 21 Ph H H H H H H Ph H H H H H Me
19-1 22 Ph H H H H H H H Ph H H H H Me
19-1 23 Ph H H H H H H H H Ph H H H Me
19-1 24 Ph H H H H H H H H H Ph H H Me
19-1 25 Ph H H H H H H H H H H Ph H Me
19-1 26 Ph H H H H H H H H H H H Ph Me
19-1 27 Me Me H H H H H H H H H H H Me
19-1 28 Me Me H H H H H Me H H H H H Me
19-1 29 Me Me H H H H H H Me H H H H Me
19-1 30 Me Me H H H H H H H Me H H H Me
19-1 31 Me Me H H H H H H H H Me H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9-1 32 Me Me H H H H H H H H H Me H Me 9-1 33 Me Me H H H H H H H H H H Me Me 9-1 34 Me Me H H H H H Ph H H H H H Me
.9-1 35 Me Me H H H H H H Ph H H H H Me
.9-1 36 Me Me H H H H H H H Ph H H H Me 9-1 37 Me Me H H H H H H H H Ph H H Me
.9-1 38 Me Me H H H H H H H H H Ph H Me
.9-1 39 Me Me H H H H H H H H H H Ph Me
.9-1 40 Ph Me H H H H H H H H H H H Me
.9-1 41 Ph Me H H H H H Me H H H H H Me
.9-1 42 Ph Me H H H H H H Me H H H H Me
.9-1 43 Ph Me H H H H H H H Me H H H Me
.9-1 44 Ph Me H H H H H H H H Me H H Me
.9-1 45 Ph Me H H H H H H H H H Me H Me
.9-1 46 Ph Me H H H H H H H H H H Me Me
.9-1 47 Ph Me H H H H H Ph H H H H H Me
.9-1 48 Ph Me H H H H H H Ph H H H H Me
.9-1 49 Ph Me H H H H H H H Ph H H H Me
.9-1 50 Ph Me H H H H H H H H Ph H H Me
.9-1 51 Ph Me H H H H H H H H H Ph H Me
.9-1 52 Ph Me H H H H H H H H H H Ph Me
9-1 53 Me H Me H H H H H H H H H H Me 9-1 54 Me H Me H H H H Me H H H H H Me 9-1 55 Me H Me H H H H H Me H H H H Me 9-1 56 Me H Me H H H H H H Me H H H Me 9-1 57 Me H Me H H H H H H H Me H H Me 9-1 58 Me H Me H H H H H H H H Me H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7
19-1 59 Me H Me H H H H H H H H H Me Me
19-1 60 Me H Me H H H H Ph H H H H H Me
19-1 61 Me H Me H H H H H Ph H H H H Me
19-1 62 Me H Me H H H H H H Ph H H H Me
19-1 63 Me H Me H H H H H H H Ph H H Me
19-1 64 Me H Me H H H H H H H H Ph H Me
19-1 65 Me H Me H H H H H H H H H Ph Me
19-1 66 Ph H Me H H H H H H H H H H Me
19-1 67 Ph H Me H H H H Me H H H H H Me
19-1 68 Ph H Me H H H H H Me H H H H Me
19-1 69 Ph H Me H H H H H H Me H H H Me
19-1 70 Ph H Me H H H H H H H Me H H Me
19-1 71 Ph H Me H H H H H H H H Me H Me
19-1 72 Ph H Me H H H H H H H H H Me Me
19-1 73 Ph H Me H H H H Ph H H H H H Me
19-1 74 Ph H Me H H H H H Ph H H H H Me
19-1 75 Ph H Me H H H H H H Ph H H H Me
19-1 76 Ph H Me H H H H H H H Ph H H Me
19-1 77 Ph H Me H H H H H H H H Ph H Me
19-1 78 Ph H Me H H H H H H H H H Ph Me
9-1 79 Me H H Me H H H H H H H H H Me 9-1 80 Me H H Me H H H Me H H H H H Me 9-1 81 Me H H Me H H H H Me H H H H Me 9-1 82 Me H H Me H H H H H Me H H H Me 9-1 83 Me H H Me H H H H H H Me H H Me 9-1 84 Me H H Me H H H H H H H Me H Me 9-1 85 Me H H Me H H H H H H H H Me Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9-1 86 Me H H Me H H H Ph H H H H H Me 9-1 87 Me H H Me H H H H Ph H H H H Me 9-1 88 Me H H Me H H H H H Ph H H H Me 9-1 89 Me H H Me H H H H H H Ph H H Me 9-1 90 Me H H Me H H H H H H H Ph H Me 9-1 91 Me H H Me H H H H H H H H Ph Me 9-1 92 Ph H H Me H H H H H H H H H Me 9-1 93 Ph H H Me H H H Me H H H H H Me 9-1 94 Ph H H Me H H H H Me H H H H Me 9-1 95 Ph H H Me H H H H H Me H H H Me 9-1 96 Ph H H Me H H H H H H Me H H Me 9-1 97 Ph H H Me H H H H H H H Me H Me 9-1 98 Ph H H Me H H H H H H H H Me Me .9-1 99 Ph H H Me H H H Ph H H H H H Me .9-1 100 Ph H H Me H H H H Ph H H H H Me .9-1 101 Ph H H Me H H H H H Ph H H H Me .9-1 102 Ph H H Me H H H H H H Ph H H Me 9-1 103 Ph H H Me H H H H H H H Ph H Me .9-1 104 Ph H H Me H H H H H H H H Ph Me
9-1 105 Me H H H Me H H H H H H H H Me 9-1 106 Me H H H Me H H Me HH H H H H Me 9-1 107 Me H H H Me H H H Me H H H H Me 9-1 108 Me H H H Me H H H H Me H H H Me 9-1 109 Me H H H Me H H H H H Me H H Me 9-1 110 Me H H H Me H H H H H H Me H Me 9-1 111 Me H H H Me H H H H H H H Me Me 9-1 112 Me H H H Me H H Ph H H H H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9-1 113 Me H H H Me H H H Ph H H H H Me 9-1 114 Me H H H Me H H H H Ph H H H Me 9-1 115 Me H H H Me H H H H H Ph H H Me 9-1 116 Me H H H Me H H H H H H Ph H Me 9-1 117 Me H H H Me H H H H H H H Ph Me 9-1 118 Ph H H H Me H H H H H H H H Me 9-1 119 Ph H H H Me H H Me H H H H H Me 9-1 120 Ph H H H Me H H H Me H H H H Me 9-1 121 Ph H H H Me H H H H Me H H H Me 9-1 122 Ph H H H Me H H H H H Me H H Me 9-1 123 Ph H H H Me H H H H H H Me H Me 9-1 124 Ph H H H Me H H H H H H H Me Me 9-1 125 Ph H H H Me H H Ph H H H H H Me 9-1 126 Ph H H H Me H H H Ph H H H H Me 9-ϊ 127 Ph H H H Me H H H H Ph H H H Me 9-1 128 Ph H H H Me H H H H H Ph H H Me 9-1 129 Ph H H H Me H H H H H H Ph H Me 9-1 130 Ph H H H Me H H H H H H H Ph Me
19-1 131 Me H H H H Me H H H H H H H Me
19-1 132 Me H H H H Me H Me H H H H H Me
19-1 133 Me H H H H Me H H Me H H H H Me
19-1 134 Me H H H H Me H H H Me H H H Me
19-1 135 Me H H H H Me H H H H Me H H Me
19-1 136 Me H H H H Me H H H H H Me H Me
19-1 137 Me H H H H Me H H H H H H Me Me
19-1 138 Me H H H H Me H Ph H H H H H Me
19-1 139 Me H H H H Me H H Ph H H H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7
19-1 140 Me H H H H Me H H H Ph H H H Me
19-1 141 Me H H H H Me H H H H Ph H H Me
19-1 142 Me H H H H Me H H H H H Ph H Me
19-1 143 Me H H H H Me H H H H H H Ph Me
19-1 144 Ph H H H H Me H H H H H H H Me
19-1 145 Ph H H H H Me H Me H H H H H Me
19-1 146 Ph H H H H Me H H Me H H H H Me
19-1 147 Ph H H H H Me H H H Me H H H Me
19-1 148 Ph H H H H Me H H H H Me H H Me
19-1 149 Ph H H H H Me H H H H H Me H Me
19-1 150 Ph H H H H Me H H H H H H Me Me
19-1 151 Ph H H H H Me H Ph H H H H H Me
19-1 152 Ph H H H H Me H H Ph H H H H Me
19-1 153 Ph H H H H Me H H H Ph H H H Me
19-1 154 Ph H H H H Me H H H H Ph H H Me
19-1 155 Ph H H H H Me H H H H H Ph H Me
19-1 156 Ph H H H H Me H H H H H H Ph Me
9-1 157 Me H H H H H Me H H H H H H Me 9-1 158 Me H H H H H Me Me H H H H H Me 9-1 159 Me H H H H H Me H Me H H H H Me 9-1 160 Me H H H H H Me H H Me H H H Me 9-1 161 Me H H H H H Me H H H Me H H Me 9-1 162 Me H H H H H Me H H H H Me H Me 9-1 163 Me H H H H H Me H H H H H Me Me 9-1 164 Me H H H H H Me Ph H H H H H Me 9-1 165 Me H H H H H Me H Ph H H H H Me 9-1 166 Me H H H H H Me H H Ph H H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7
19-1 167 Me H H H H H Me H H H Ph H H Me
19-1 168 Me H H H H H Me H H H H Ph H Me
19-1 169 Me H H H H H Me H H H H H Ph Me
19-1 170 Ph H H H H H Me H H H H H H Me
19-1 171 Ph H H H H H Me Me H H H H H Me
19-1 172 Ph H H H H H Me H Me H H H H Me
19-1 173 Ph H H H H H Me H H Me H H H Me
19-1 174 Ph H H H H H Me H H H Me H H Me
19-1 175 Ph H H H H H Me H H H H Me H Me
19-1 176 Ph H H H H H Me H H H H H Me Me
19-1 177 Ph H H H H H Me Ph H H H H H Me
19-1 178 Ph H H H H H Me H Ph H H H H Me
19-1 179 Ph H H H H H Me H H Ph H H H Me
19-1 180 Ph H H H H H Me H H H Ph H H Me
19-1 181 Ph H H H H H Me H H H H Ph H Me
19-1 182 Ph H H H H H Me H H H H H Ph Me
9-1 1 83 Me Ph H H H H H H H H H H H Me 9-1 1 84 Me Ph H H H H H Me H H H H H Me 9-1 ] 85 Me Ph H H H H H H Me H H H H Me 9-1 ] 86 Me Ph H H H H H H H Me H H H Me 9-1 1 87 Me Ph H H H H H H H H Me H H Me 9-1 ] 88 Me Ph H H H H H H H H H Me H Me 9-1 ] 189 Me Ph H H H H H H H H H H Me Me 9-1 1 190 Me Ph H H H H H Ph H H H H H Me 9-1 191 Me Ph H H H H H H Ph H H H H Me 9-1 192 Me Ph H H H H H H H Ph H H H Me 9-1 193 Me Ph H H H H H H H H Ph H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7
19-1 194 Me Ph H H H H H H H H H Ph H Me
19-1 195 Me Ph H H H H H H H H H H Ph Me
19-1 196 Ph Ph H H H H H H H H H H H Me
19-1 197 Ph Ph H H H H H Me H H H H H Me
19-1 198 Ph Ph H H H H H H Me H H H H Me
19-1 199 Ph Ph H H H H H H H Me H H H Me
19-1 200 Ph Ph H H H H H H H H Me H H Me
19-1 201 Ph Ph H H H H H H H H H Me H Me
19-1 202 Ph Ph H H H H H H H H H H Me Me
19-1 203 Ph Ph H H H H H Ph H H H H H Me
19-1 204 Ph Ph H H H H H H Ph H H H H Me
19-1 205 Ph Ph H H H H H H H Ph H H H Me
19-1 206 Ph Ph H H H H H H H H Ph H H Me
19-1 207 Ph Ph H H H H H H H H H Ph H Me
19-1 208 Ph Ph H H H H H H H H H H Ph Me
9-1 209 Me H Ph H H H H H H H H H H Me 9-1 210 Me H Ph H H H H Me H H H H H Me 9-1 211 Me H Ph H H H H H Me H H H H Me 9-1 212 Me H Ph H H H H H H Me H H H Me 9-1 213 Me H Ph H H H H H H H Me H H Me 9-1 214 Me H Ph H H H H H H H H Me H Me 9-1 215 Me H Ph H H H H H H H H H Me Me 9-1 216 Me H Ph H H H H Ph H H H H H Me 9-1 217 Me H Ph H H H H H Ph H H H H Me 9-1 218 Me H Ph H H H H H H Ph H H H Me 9-1 219 Me H Ph H H H H H H H Ph H H Me 9-1 220 Me H Ph H H H H H H H H Ph H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9-1 221 Me H Ph H H H H H H H H H Ph Me 9-1 222 Ph H Ph H H H H H H H H H H Me 9-1 223 Ph H Ph H H H H Me H H H H H Me .9-1 224 Ph H Ph H H H H H Me H H H H Me 9-1 225 Ph H Ph H H H H H H Me H H H Me .9-1 226 Ph H Ph H H H H H H H Me H H Me .9-1 227 Ph H Ph H H H H H H H H Me H Me 9-1 228 Ph H Ph H H H H H H H H H Me Me .9-1 229 Ph H Ph H H H H Ph H H H H H Me .9-1 230 Ph H Ph H H H H H Ph H H H H Me .9-1 231 Ph H Ph H H H H H H Ph H H H Me .9-1 232 Ph H Ph H H H H H H H Ph H H Me [9-1 233 Ph H Ph H H H H H H H H Ph H Me .9-1 234 Ph H Ph H H H H H H H H H Ph Me
9-1 235 Me H H Ph H H H H H H H H H Me 9-1 236 Me H H Ph H H H Me H H H H H Me 9-1 237 Me H H Ph H H H H Me H H H H Me 9-1 238 Me H H Ph H H H H H Me H H H Me 9-1 239 Me H H Ph H H H H H H Me H H Me 9-1 240 Me H H Ph H H H H H H H Me H Me 9-1 241 Me H H Ph H H H H H H H H Me Me 9-1 242 Me H H Ph H H H Ph H H H H H Me 9-1 243 Me H H Ph H H H H Ph H H H H Me 9-1 244 Me H H Ph H H H H H Ph H H H Me .9-1 245 Me H H Ph H H H H H H Ph H H Me 9-1 246 Me H H Ph H H H H H H H Ph H Me .9-1 247 Me H H Ph H H H H H H H H Ph Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9-1 248 Ph H H Ph H H H H H H H H H Me 9-1 249 Ph H H Ph H H H Me H H H H H Me 9-1 250 Ph H H Ph H H H H Me H H H H Me 9-1 251 Ph H H Ph H H H H H Me H H H Me 9-1 252 Ph H H Ph H H H H H H Me H H Me 9-1 253 Ph H H Ph H H H H H H H Me H Me 9-1 254 Ph H H Ph H H H H H H H H Me Me 9-1 255 Ph H H Ph H H H Ph H H H H H Me 9-1 256 Ph H H Ph H H H H Ph H H H H Me 9-1 257 Ph H H Ph H H H H H Ph H H H Me 9-1 258 Ph H H Ph H H H H H H Ph H H Me 9-1 259 Ph H H Ph H H H H H H H Ph H Me 9-1 260 Ph H H Ph H H H H H H H H Ph Me
19-1 261 Me H H H Ph H H H H H H H H Me
19-1 262 Me H H H Ph H H Me H H H H H Me
19-1 263 Me H H H Ph H H H Me H H H H Me
19-1 264 Me H H H Ph H H H H Me H H H Me
19-1 265 Me H H H Ph H H H H H Me H H Me
19-1 266 Me H H H Ph H H H H H H Me H Me
19-1 267 Me H H H Ph H H H H H H H Me Me
19-1 268 Me H H H Ph H H Ph H H H H H Me
19-1 269 Me H H H Ph H H H Ph H H H H Me
19-1 270 Me H H H Ph H H H H Ph H H H Me
19-1 271 Me H H H Ph H H H H H Ph H H Me
19-1 272 Me H H H Ph H H H H H H Ph H Me
19-1 273 Me H H H Ph H H H H H H H Ph Me
19-1 274 Ph H H H Ph H H H H H H H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7
19-1 275 Ph H H H Ph H H Me H H H H H Me
19-1 276 Ph H H H Ph H H H Me H H H H Me
19-1 277 Ph H H H Ph H H H H Me H H H Me
19-1 278 Ph H H H Ph H H H H H Me H H Me
19-1 279 Ph H H H Ph H H H H H H Me H Me
19-1 280 Ph H H H Ph H H H H H H H Me Me
19-1 281 Ph H H H Ph H H Ph H H H H H Me
19-1 282 Ph H H H Ph H H H Ph H H H H Me
19-1 283 Ph H H H Ph H H H H Ph H H H Me
19-1 284 Ph H H H Ph H H H H H Ph H H Me
19-1 285 Ph H H H Ph H H H H H H Ph H Me
19-1 286 Ph H H H Ph H H H H H H H Ph Me
9-1 287 Me H H H H Ph H H H H H H H Me 9-1 288 Me H H H H Ph H Me H H H H H Me 9-1 289 Me H H H H Ph H H Me H H H H Me 9-1 290 Me H H H H Ph H H H Me H H H Me 9-1 291 Me H H H H Ph H H H H Me H H Me 9-1 292 Me H H H H Ph H H H H H Me H Me 9-1 293 Me H H H H Ph H H H H H H Me Me 9-1 294 Me H H H H Ph H Ph H H H H H Me 9-1 295 Me H H H H Ph H H Ph H H H H Me 9-1 296 Me H H H H Ph H H H Ph H H H Me 9-1 297 Me H H H H Ph H H H H Ph H H Me 9-1 298 Me H H H H Ph H H H H H Ph H Me 9-1 299 Me H H H H Ph H H H H H H Ph Me 9-1 300 Ph H H H H Ph H H H H H H H Me 9-1 301 Ph H H H H Ph H Me H H H H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 9-1 302 Ph H H H H Ph H H Me H H H H Me 9-1 303 Ph H H H H Ph H H H Me H H H Me 9-1 304 Ph H H H H Ph H H H H Me H H Me 9-1 305 Ph H H H H Ph H H H H H Me H Me 9-1 306 Ph H H H H Ph H H H H H H Me Me 9-1 307 Ph H H H H Ph H Ph H H H H H Me 9-1 308 Ph H H H H Ph H H Ph H H H H Me 9-1 309 Ph H H H H Ph H H H Ph H H H Me 9-1 310 Ph H H H H Ph H H H H Ph H H Me 9-1 311 Ph H H H H Ph H H H H H Ph H Me 9-1 312 Ph H H H H Ph H H H H H H Ph Me
19-1 313 Me H H H H H Ph H H H H H H Me
19-1 314 Me H H H H H Ph Me H H H H H Me
19-1 315 Me H H H H H Ph H Me H H H H Me
19-1 316 Me H H H H H Ph H H Me H H H Me
19-1 317 Me H H H H H Ph H H H Me H H Me
19-1 318 Me H H H H H Ph H H H H Me H Me
19-1 319 Me H H H H H Ph H H H H H Me Me
19-1 320 Me H H H H H Ph Ph H H H H H Me
19-1 321 Me H H H H H Ph H Ph H H H H Me
19-1 322 Me H H H H H Ph H H Ph H H H Me
19-1 323 Me H H H H H Ph H H H Ph H H Me
19-1 324 Me H H H H H Ph H H H H Ph H Me
19-1 325 Me H H H H H Ph H H H H H Ph Me
19-1 326 Ph H H H H H Ph H H H H H H Me
19-1 327 Ph H H H H H Ph Me H H H H H Me
19-1 328 Ph H H H H H Ph H Me H H H H Me Cpd No. Rai Ra2 Ra3 Rb4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7
19-1329 Ph H H H H H Ph H H Me H H H Me
19-1330 Ph H H H H H Ph H H H Me H H Me
19-1331 Ph H H H H H Ph H H H H Me H Me
19-1332 Ph H H H H H Ph H H H H H Me Me
19-1333 Ph H H H H H Ph Ph H H H H H Me
19-1334 Ph H H H H H Ph H Ph H H H H Me
19-1335 Ph H H H H H Ph H H Ph H H H Me
19-1336 Ph H H H H H Ph H H H Ph H H Me
19-1337 Ph H H H H H Ph H H H H Ph H Me
19-1338 Ph H H H H H Ph H H H H H Ph Me
Table 20
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 20-1 Me H H H H H H H H H H H H H H 20-2 Me H H H H H H Me H H H H H H H 20-3 Me H H H H H H H Me H H H H H H 20-4 Me H H H H H H H H Me H H H H H 20-5 Me H H H H H H H H H Me H H H H 20-6 Me H H H H H H H H H H Me H H H 20-7 Me H H H H H H H H H H H Me H H 20-8 Me H H H H H H H H H H H H Me H 20-9 Me H H H H H H H H H H H H H Me 20- 10 Me H H H H H H Ph H H H H H H H 20-11 Me H H H H H H H Ph H H H H H H 20- 12 Me H H H H H H H H Ph H H H H H 20- 13 Me H H H H H H H H H Ph H H H H 20- 14 Me H H H H H H H H H H Ph H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 20-15 Me H H H H H H H H H H H Ph H H 20-16 Me H H H H H H H H H H H H Ph H 20-17 Me H H H H H H H H H H H H H Ph 20- 18 , Ph H H H H H H H H H H H H H H 20-19 Ph H H H H H H Me H H H H H H H 20-20 Ph H H H H H H H Me H H H H H H 20-21 Ph H H H H H H H H Me H H H H H 20-22 Ph H H H H H H H H H Me H H H H 20-23 Ph H H H H H H H H H H Me H H H 20-24 Ph H H H H H H H H H H H Me H H 20-25 Ph H H H H H H H H H H H H Me H 20-26 Ph H H H H HH H H H H H H H H Me 20-27 Ph H H H H HH H Ph H H H H H H H 20-28 Ph H H H H HH H H Ph H H H H H H 20-29 Ph H H H H H H H H Ph H H H H H 20-30 Ph H H H H H H H H H Ph H H H H 20-31 Ph H H H H H H H H H H Ph H H H 20-32 Ph H H H H H H H H H H H Ph H H 20-33 Ph H H H H H H H H H H H H Ph H 20-34 Ph H H H H H H H H H H H H H Ph
20-35 Me Me H H H H H H H H H H H H H 20-36 Me Me H H H H H Me H H H H H H H 20-37 Me Me H H H H H H Me H H H H H H 20-38 Me Me H H H H H H H Me H H H H H 20-39 Me Me H H H H H H H H Me H H H H 20-40 Me Me H H H H H H H H H Me H H H 20-41 Me Me H H H H H H H H H H Me H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 20-42 Me Me H H H H HH H H H H H H Me H 20-43 Me Me H H H H H H H H H H H H Me 20-44 Me Me H H H H H Ph H H H H H H H 20-45 Me Me H H H H H H Ph H H H H H H 20-46 Me Me H H H H HH H H Ph H H H H H 20-47 Me Me H H H H H H H H H Ph H H H H 20-48 Me Me H H H H HH H H H H Ph H H H 20-49 Me Me H H H H H H H H H H H Ph H H 20-50 Me Me H H H H H H H H H H H H Ph H 20-51 Me Me H H H H H H H H H H H H H Ph 20-52 Ph Me H H H H H H H H H H H H H H 20-53 Ph Me H H H H H H Me H H H H H H H 20-54 Ph Me H H H H H H H Me H H H H H H 20-55 Ph Me H H H H H H H H Me H H H H H 20-56 Ph Me H H H H H H H H H Me H H H H 20-57 Ph Me H H H H H H H H H Me H H H 20-58 Ph Me H H H H H H H H H H Me H H 20-59 Ph Me H H H H H H H H H H H Me H 20-60 Ph Me H H H H H H H H H H H H Me 20-61 Ph Me H H H H H Ph H H H H H H H 20-62 Ph Me H H H H H H Ph H H H H H H 20-63 Ph Me H H H H H H H Ph H H H H H 20-64 Ph Me H H H H H H H H Ph H H H H 20-65 Ph Me H H H H H H H H H Ph H H H 20-66 Ph Me H H H H H H H H H H Ph H H 20-67 Ph Me H H H H H H H H H H H Ph H 20-68 Ph Me H H H H H H H H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 R Rbb66 Rb7 Rb8 20-69 Me H Me H H H H H H H H H H H H 20-70 Me H Me H H H H Me H H H H H H H 20-71 Me H Me H H H H H Me H H H H H H 20-72 Me H Me H H H H H HH MMee HH HH H H H 20-73 Me H Me H H H H H HH HH MMee HH H H H 20-74 Me H Me H H H H H HH HH HH MMee H H H 20-75 Me H Me H H H H H HH HH HH HH Me H H 20-76 Me H Me H H H H H HH HH HH HH H Me H 20-77 Me H Me H H H H H H H H H H H Me 20-78 Me H Me H H H H Ph H H H H H H H 20-79 Me H Me H H H H H Ph H H H H H H 20-80 Me H Me H H H H H H Ph H H H H H 20-81 Me H Me H H H H H H H Ph H H H H 20-82 Me H Me H H H H H H H H Ph H H H 20-83 Me H Me H H H H H H H H H Ph H H 20-84 Me H Me H H H H H H H H H H Ph H 20-85 Me H Me H H H H H H H H H H H Ph 20-86 Ph H Me H H H H H H H H H H H H 20-87 Ph H Me H H H H Me H H H H H H H 20-88 Ph H Me H H H H H Me H H H H H H 20-89 Ph H Me H H H H H H Me H H H H H 20-90 Ph H Me H H H H H H H Me H H H H 20-91 Ph H Me H H H H H H H H Me H H H 20-92 Ph H Me H H H H H H H H H Me H H 20-93 Ph H Me H H H H H H H H H H Me H 20-94 Ph H Me H H H H H H H H H H H Me 20-95 Ph H Me H H H H Ph H H H H H H H 20-96 Ph H Me H H H H H Ph H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 20- 97 Ph H Me H H H H H H Ph H H H H H 20- 98 Ph H Me H H H H H H H Ph H H H H 20- 99 Ph H Me H H H H H H H H Ph H H H 20- 100 Ph H Me H H H H H H H H H Ph H H 20- 101 Ph H Me H H H H H H H H H H Ph H 20- 102 Ph H Me H H H H H H H H H H H Ph
20- 103 Me H H Me H H H H H H H H H H H 20- 104 Me H H Me H H H Me H H H H H H H 20- 105 Me H H Me H H H H Me H H H H H H 20- 106 Me H H Me H H H H H Me H H H H H 20- 107 Me H H Me H H H H H H Me H H H H 20- 108 Me H H Me H H H H H H H Me H H H 20- 109 Me H H Me H H H H H H H H Me H H 20- 110 Me H H Me H H H H H H H H H Me H 20- 111 Me H H Me H H H H H H H H H H Me 20- 112 Me H H Me H H H Ph H H H H H H H 20- 113 Me H H Me H H H H Ph H H H H H H 20- 114 Me H H Me H H H H H Ph H H H H H 20- 115 Me H H Me H H H H H H Ph H H H H 20- 116 Me H H Me H H H H H H H Ph H H H 20- 117 Me H H Me H H H H H H H H Ph H H 20- 118 Me H H Me H H H H H H H H H Ph H 20- 119 Me H H Me H H H H H H H H H H Ph 20- 120 Ph H H Me H H H H H H H H H H H 20- 121 Ph H H Me H H H Me H H H H H H H 20- 122 Ph H H Me H H H H Me H H H H H H 20- 123 Ph H H Me H H H H H Me H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 20- 124 Ph H H Me H H H H H H Me H H H H 20- 125 Ph H H Me H H H H H H H Me H H H 20- 126 Ph H H Me H H H H H H H H Me H H 20- 127 Ph H H Me H H H H H H H H H Me H 20- 128 Ph H H Me H H H H H H H H H H Me 20- 129 Ph H H Me H H H Ph H H H H H H H 20- 130 Ph H H Me H H H H Ph H H H H H H 20- 131 Ph H H Me H H H H H Ph H H H H H 20- 132 Ph H H Me H H H H H H Ph H H H H 20- 133 Ph H H Me H H H H H H H Ph H H H 20- 134 Ph H H Me H H H H H H H H Ph H H 20- 135 Ph H H Me H H H H H H H H H Ph H 20- 136 Ph H H Me H H H H H H H H H H Ph
20- 137 Me H H H Me H H H H H H H H H H 20- 138 Me H H H Me H H Me H H H H H H H 20- 139 Me H H H Me H H H Me H H H H H H 20-140 Me H H H Me H H H H Me H H H H H 20-141 Me H H H Me H H H H H Me H H H H 20- 142 Me H H H Me H H H H H H Me H H H 20- 143 Me H H H Me H H H H H H H Me H H 20- 144 Me H H H Me H H H H H H H H Me H 20- 145 Me H H H Me H H H H H H H H H Me 20-146 Me H H H Me H H Ph H H H H H H H 20- 147 Me H H H Me H H H Ph H H H H H H 20- 148 Me H H H Me H H H H Ph H H H H H 20-149 Me H H H Me H H H H H Ph H H H H 20-150 Me H H H Me H H H H H H Ph H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 20- 151 Me H H H Me H H H H H H H Ph H H 20- 152 Me H H H Me H H H H H H H H Ph H 20- 153 Me H H H Me H H H H H H H H H Ph 20- 154 Ph H H H Me H H H H H H H H H H 20- 155 Ph H H H Me H H Me H H H H H H H 20- 156 Ph H H H Me H H H Me H H H H H H 20- 157 Ph H H H Me H H H H Me H H H H H 20- 158 Ph H H H Me H H H H H Me H H H H 20- 159 Ph H H H Me H H H H H H Me H H H 20- 160 Ph H H H Me H H H H H H H Me H H 20- 161 Ph H H H Me H H H H H H H H Me H 20- 162 Ph H H H Me H H H H H H H H H Me 20- 163 Ph H H H Me H H Ph H H H H H H H 20- 164 Ph H H H Me H H H Ph H H H H H H 20- 165 Ph H H H Me H H H H Ph H H H H H 20- 166 Ph H H H Me H H H H H Ph H H H H 20- 167 Ph H H H Me H H H H H H Ph H H H 20- 168 Ph H H H Me H H H H H H H Ph H H 20- 169 Ph H H H Me H H H H H H H H Ph H 20- 170 Ph H H H Me H H H H H H H H H Ph
20- 171 Me H H H H Me H H H H H H H H H 20- 172 Me H H H H Me H Me H H H H H H H 20- 173 Me H H H H Me H H Me H H H H H H 20- 174 Me H H H H Me H H H Me H H H H H 20- 175 Me H H H H Me H H H H Me H H H H 20- 176 Me H H H H Me H H H H H Me H H H 20- 177 Me H H H H Me H H H H H H Me H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 20- 178 Me H H H H Me H H H H H H H Me H 20- 179 Me H H H H Me H H H H H H H H Me 20- 180 Me H H H H Me H Ph H H H H H H H 20- 181 Me H H H H Me H H Ph H H H H H H 20- 182 Me H H H H Me H H H Ph H H H H H 20- 183 Me H H H H Me H H H H Ph H H H H 20- 184 Me H H H H Me H H H H H Ph H H H 20- 185 Me H H H H Me H H H H H H Ph H H 20- 186 Me H H H H Me H H H H H H H Ph H 20- 187 Me H H H H Me H H HH HH HH HH H H Ph 20- 188 Ph H H H H Me H H H H H H H H H 20- 189 Ph H H H H Me H Me H H H H H H H 20- 190 Ph H H H H Me H H Me H H H H H H 20- 191 Ph H H H H Me H H H Me H H H H H 20- 192 Ph H H H H Me H H H H Me H H H H 20- 193 Ph H H H H Me H H H H H Me H H H 20- 194 Ph H H H H Me H H H H H H Me H H 20- 195 Ph H H H H Me H H H H H H H Me H 20- 196 Ph H H H H Me H H H H H H H H Me 20- 197 Ph H H H H Me H Ph H H H H H H H 20- 198 Ph H H H H Me H H Ph H H H H H H 20- 199 Ph H H H H Me H H H Ph H H H H H 20- 200 Ph H H H H Me H H H H Ph H H H H 20- 201 Ph H H H H Me H H H H H Ph H H H 20- 202 Ph H H H H Me H H H H H H Ph H H 20- 203 Ph H H H H Me H H H H H H H Ph H 20- 204 Ph H H H H Me H H H H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 R Rbb66 Rb7 Rb8 20- 205 Me H H H H H Me H HH HH HH HH H H H 20- 206 Me H H H H H Me Me HH HH HH HH H H H 20- 207 Me H H H H H Me H MMee HH HH HH H H H 20- 208 Me H H H H H Me H HH MMee HH HH H H H 20- 209 Me H H H H H Me H HH HH MMee HH H H H 20- 210 Me H H H H H Me H HH HH HH MMee H H H 20- 211 Me H H H H H Me H H H H H Me H H 20- 212 Me H H H H H Me H H H H H H Me H 20- 213 Me H H H H H Me H H H H H H H Me 20- 214 Me H H H H H Me Ph H H H H H H H 20- 215 Me H H H H H Me H Ph H H H H H H 20- 216 Me H H H H H Me H H Ph H H H H H 20- 217 Me H H H H H Me H H H Ph H H H H 20- 218 Me H H H H H Me H H H H Ph H H H 20- 219 Me H H H H H Me H H H H H Ph H H 20- 220 Me H H H H H Me H H H H H H Ph H 20- 221 Me H H H H H Me H H H H H H H Ph 20- 222 Ph H H H H H Me H H H H H H H H 20- 223 Ph H H H H H Me Me H H H H H H H 20- 224 Ph H H H H H Me H Me H H H H H H 20- 225 Ph H H H H H Me H H Me H H H H H 20- 226 Ph H H H H H Me H H H Me H H H H 20- 227 Ph H H H H H Me H H H H Me H H H 20- 228 Ph H H H H H Me H H H H H Me H H 20- 229 Ph H H H H H Me H HH HH HH HH H Me H 20- 230 Ph H H H H H Me H H H H H H H Me 20- 231 Ph H H H H H Me Ph H H H H H H H 20- 232 Ph H H H H H Me H Ph H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 20-233 Ph H H H H H Me H H Ph H H H H H 20-234 Ph H H H H H Me H H H Ph H H H H 20-235 Ph H H H H H Me H H H H Ph H H H 20-236 Ph H H H H H Me H H H H H Ph H H 20-237 Ph H H H H H Me H H H H H H Ph H 20-238 Ph H H H H H Me H H H H H H H Ph
20-239 Me Ph H H H H H H H H H H H H H 20-240 Me Ph H H H H H Me H H H H H H H 20-241 Me Ph H H H H H H Me H H H H H H 20-242 Me Ph H H H H H H H Me H H H H H 20-243 Me Ph H H H H H H H H Me H H H H 20-244 Me Ph H H H H H H H H H Me H H H 20-245 Me Ph H H H H H H H H H H Me H H 20-246 Me Ph H H H H H H H H H H H Me H 20-247 Me Ph H H H H H H H H H H H H Me 20-248 Me Ph H H H H H Ph H H H H H H H 20-249 Me Ph H H H H H H Ph H H H H H H 20-250 Me Ph H H H H H H H Ph H H H H H 20-251 Me Ph H H H H H H H H Ph H H H H 20-252 Me Ph H H H H H H H H H Ph H H H 20-253 Me Ph H H H H H H H H H H Ph H H 20-254 Me Ph H H H H H H H H H H H Ph H 20-255 Me Ph H H H H H H H H H H H H Ph 20-256 Ph Ph H H H H H H H H H H H H H 20-257 Ph Ph H H H H H Me H H H H H H H 20-258 Ph Ph H H H H H H Me H H H H H H 20-259 Ph Ph H H H H H H H Me H H H H H I Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8- 260 Ph Ph H H H H H H H H Me H H H H- 261 Ph Ph H H H H H H H H H Me H H H- 262 Ph Ph H H H H H H H H H H Me H H- 263 Ph Ph H H H H H H H H H H H Me H- 264 Ph Ph H H H H H H H H H H H H Me- 265 Ph Ph H H H H H Ph H H H H H H H- 266 Ph Ph H H H H H H Ph H H H H H H- 267 Ph Ph H H H H H H H Ph H H H H H- 268 Ph Ph H H H H H H H H Ph H H H H- 269 Ph Ph H H H H H H H H H Ph H H H- 270 Ph Ph H H H H H H H H H H Ph H H- 271 Ph Ph H H H H H H H H H H H Ph H- 272 Ph Ph H H H H H H H H H H H H Ph - 273 Me H Ph H H H H H H H H H H H H- 274 Me H Ph H H H H Me H H H H H H H- 275 Me H Ph H H H H H Me H H H H H H- 276 Me H Ph H H H H H H Me H H H H H- 277 Me H Ph H H H H H H H Me H H H H- 278 Me H Ph H H H H H H H H Me H H H- 279 Me H Ph H H H H H H H H H Me H H- 280 Me H Ph H H H H H H H H H H Me H- 281 Me H Ph H H H H H H H H H H H Me- 282 Me H Ph H H H H Ph H H H H H H H- 283 Me H Ph H H H H H Ph H H H H H H- 284 Me H Ph H H H H H H Ph H H H H H- 285 Me H Ph H H H H H H H Ph H H H H- 286 Me H Ph H H H H H H H H Ph H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 RRbb66 Rb7 Rb8 20- 287 Me H Ph H H H H H H H H H Ph H H 20- 288 Me H Ph H H H H H H H H H H Ph H 20- 289 Me H Ph H H H H H H H H H H H Ph 20- 290 Ph H Ph H H H H H H H H H H H H 20- 291 Ph H Ph H H H H Me H H H H H H H 20- 292 Ph H Ph H H H H H Me H H H H H H 20- 293 Ph H Ph H H H H H H Me H H H H H 20- 294 Ph H Ph H H H H H H H Me H H H H 20- 295 Ph H Ph H H H H H H H H Me H H H 20- 296 Ph H Ph H H H H H H H H H Me H H 20- 297 Ph H Ph H H H H H H H H H H Me H 20- 298 Ph H Ph H H H H H H H H H H H Me 20- 299 Ph H Ph H H H H Ph H H H H H H H 20- 300 Ph H Ph H H H H H Ph H H H H H H 20- 301 Ph H Ph H H H H H H Ph H H H H H 20- 302 Ph H Ph H H H H H H H Ph H H H H 20- 303 Ph H Ph H H H H H H H H Ph H H H 20- 304 Ph H Ph H H H H H H H H H Ph H H 20- 305 Ph H Ph H H H H H H H H H H Ph H 20- 306 Ph H Ph H H H H H H H H H H H Ph
20-307 Me H H Ph H H H H H H H H H H H 20-308 Me H H Ph H H H Me H H H H H H H 20-309 Me H H Ph H H H H Me H H H H H H 20-310 Me H H Ph H H H H H Me H H H H H 20-311 Me H H Ph H H H H H H Me H H H H 20-312 Me H H Ph H H H H H H H Me H H H 20-313 Me H H Ph H H H H H H H H Me H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 20-314 Me H H Ph H H H H H H H H H Me H 20-315 Me H H Ph H H H H H H H H H H Me 20-316 Me H H Ph H H H Ph H H H H H H H 20- 317 Me H H Ph H H H H Ph H H H H H H 20-318 Me H H Ph H H H H H Ph H H H H H 20-319 Me H H Ph H H H H H H Ph H H H H 20- 320 Me H H Ph H H H H H H H Ph H H H 20- 321 Me H H Ph H H H H H H H H Ph H H 20- 322 Me H H Ph H H H H H H H H H Ph H 20- 323 Me H H Ph H H H H H H H H H H Ph 20- 324 Ph H H Ph H H H H H H H H H H H 20- 325 Ph H H Ph H H H Me H H H H H H H 20- 326 Ph H H Ph H H H H Me H H H H H H 20- 327 Ph H H Ph H H H H H Me H H H H H 20- 328 Ph H H Ph H H H H H H Me H H H H 20- 329 Ph H H Ph H H H H H H H Me H H H 20- 330 Ph H H Ph H H H H H H H H Me H H 20-331 Ph H H Ph H H H H H H H H H Me H 20- 332 Ph H H Ph H H H H H H H H H H Me 20- 333 Ph H H Ph H H H Ph H H H H H H H 20- 334 Ph H H Ph H H H H Ph H H H H H H 20- 335 Ph H H Ph H H H H H Ph H H H H H 20- 336 Ph H H Ph H H H H H H Ph H H H H 20- 337 Ph H H Ph H H H H H H H Ph H H H 20- 338 Ph H H Ph H H H H H H H H Ph H H 20- 339 Ph H H Ph H H H H H H H H H Ph H 20- 340 Ph H H Ph H H H H H H H H H H Ph Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 RRbb66 Rb7 Rb8 20- 341 Me H H H Ph H H H H H H H H H H 20- 342 Me H H H Ph H H Me H H H H H H H 20- 343 Me H H H Ph H H H Me H H H H H H 20- 344 Me H H H Ph H H H H Me H H H H H 20- 345 Me H H H Ph H H H H H Me H H H H 20- 346 Me H H H Ph H H H H H H Me H H H 20- 347 Me H H H Ph H H H H H H H Me H H 20- 348 Me H H H Ph H H H H H H H H Me H 20- 349 Me H H H Ph H H H H H H H H H Me 20- 350 Me H H H Ph H H Ph H H H H H H H 20- 351 Me H H H Ph H H H Ph H H H H H H 20- 352 Me H H H Ph H H H H Ph H H H H H 20- 353 Me H H H Ph H H H H H Ph H H H H 20- 354 Me H H H Ph H H H H H H Ph H H H 20- 355 Me H H H Ph H H H H H H H Ph H. H 20- 356 Me H H H Ph H H H H H H H H Ph H 20- 357 Me H H H Ph H H H H H H H H H Ph 20-358 Ph H H H Ph H H H H H H H H H H 20-359 Ph H H H Ph H H Me H H H H H H H 20-360 Ph H H H Ph H H H Me H H H H H H 20-361 Ph H H H Ph H H H H Me H H H H H 20-362 Ph H H H Ph H H H H H Me H H H H 20-363 Ph H H H Ph H H H H H H Me H H H 20-364 Ph H H H Ph H H H H H H H Me H H 20-365 Ph H H H Ph H H H H H H H H Me H 20-366 Ph H H H Ph H H H H H H H H H Me 20-367 Ph H H H Ph H H Ph H H H H H H H 20-368 Ph H H H Ph H H H Ph H H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 20-369 Ph H H H Ph H H H H Ph H H H H H 20-370 Ph H H H Ph H H H H H Ph H H H H 20-371 Ph H H H Ph H H H H H H Ph H H H 20-372 Ph H H H Ph H H H H H H H Ph H H 20-373 Ph H H H Ph H H H H H H H H Ph H 20-374 Ph H H H Ph H H H H H H H H H Ph
20- 375 Me H H H H Ph H H H H H H H H H 20- 376 Me H H H H Ph H Me H H H H H H H 20- 377 Me H H H H Ph H H Me H H H H H H 20- 378 Me H H H H Ph H H H Me H H H H H 20- 379 Me H H H H Ph H H H H Me H H H H 20- 380 Me H H H H Ph H H H H H Me H H H 20- 381 Me H H H H Ph H H H H H H Me H H 20- 382 Me H H H H Ph H H H H H H H Me H 20- 383 Me H H H H Ph H H H H H H H H Me 20- 384 Me H H H H Ph H Ph H H H H H H H 20- 385 Me H H H H Ph H H Ph H H H H H H 20- 386 Me H H H H Ph H H H Ph H H H H H 20- 387 Me H H H H Ph H H H H Ph H H H H 20- 388 Me H H H H Ph H H H H H Ph H H H 20- 389 Me H H H H Ph H H H H H H Ph H H 20- 390 Me H H H H Ph H H H H H H H Ph H 20- 391 Me H H H H Ph H H H H H H H H Ph 20- 392 Ph H H H H Ph H H H H H H H H H 20- 393 Ph H H H H Ph H Me H H H H H H H 20- 394 Ph H H H H Ph H H Me H H H H H H 20- 395 Ph H H H H Ph H H H Me H H H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 20- 396 Ph H H H H Ph H H H H Me H H H H 20- 397 Ph H H H H Ph H H H H H Me H H H 20- 398 Ph H H H H Ph H H H H H H Me H H 20- 399 Ph H H H H Ph H H H H H H H Me H 20- 400 Ph H H H H Ph H H H H H H H H Me 20- 401 Ph H H H H Ph H Ph H H H H H H H 20- 402 Ph H H H H Ph H H Ph H H H H H H 20- 403 Ph H H H H Ph H H H Ph H H H H H 20- 404 Ph H H H H Ph H H H H Ph H H H H 20- 405 Ph H H H H Ph H H H H H Ph H H H 20- 406 Ph H H H H Ph H H H H H H Ph H H 20- 407 Ph H H H H Ph H H H H H H H Ph H 20- 408 Ph H H H H Ph H H H H H H H H Ph
20- 409 Me H H H H H Ph H H H H H H H H 20- 410 Me H H H H H Ph Me H H H H H H H 20- 411 Me H H H H H Ph H Me H H H H H H 20- 412 Me H H H H H Ph H H Me H H H H H 20- 413 Me H H H H H Ph H H H Me H H H H 20- 414 Me H H H H H Ph H H H H Me H H H 20- 415 Me H H H H H Ph H H H H H Me H H 20- 416 Me H H H H H Ph H H H H H H Me H 20- 417 Me H H H H H Ph H H H H H H H Me 20- 418 Me H H H H H Ph Ph H H H H H H H 20- 419 Me H H H H H Ph H Ph H H H H H H 20- 420 Me H H H H H Ph H H Ph H H H H H 20- 421 Me H H H H H Ph H H H Ph H H H H 20- 422 Me H H H H H Ph H H H H Ph H H H Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 RRbb66 Rb7 Rb8 20- 423 Me H H H H H Ph H H H H H Ph H H 20- 424 Me H H H H H Ph H H H H H H Ph H 20- 425 Me H H H H H Ph H H H H H H H Ph 20- 426 Ph H H H H H Ph H H H H H H H H 20- 427 Ph H H H H H Ph Me H H H H H H H 20- 428 Ph H H H H H Ph H Me H H H H H H 20- 429 Ph H H H H H Ph H H Me H H H H H 20- 430 Ph H H H H H Ph H H H Me H H H H 20- 431 Ph H H H H H Ph H H H H Me H H H 20- 432 Ph H H H H H Ph HH H H H H Me H H 20- 433 Ph H H H H H Ph HH H H H H H Me H 20- 434 Ph H H H H H Ph HH H H H H H H Me 20- 435 Ph H H H H H Ph PPhh H H H H H H H 20- 436 Ph H H H H H Ph HH Ph H H H H H H 20- 437 Ph H H H H H Ph HH H Ph H H H H H 20- 438 Ph H H H H H Ph HH H H Ph H H H H 20- 439 Ph H H H H H Ph HH H H H Ph H H H 20- 440 Ph H H H H H Ph HH H H H H Ph H H 20- 441 Ph H H H H H Ph HH H H H H H Ph H 20- 442 Ph H H H H H Ph H H H H H H H Ph
Table 21
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 21- 1 Me H H H H H H Me 21- 2 Me H H Me H H H Me 21- 3 Me H H H Me H H Me 21- 4 Me H H H H Me H Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 21-5 Me H H H H H Me Me 21-6 Me H H Ph H H H Me 21-7 Me H H H Ph H H Me 21-8 Me H H H H Ph H Me 1 21-9 Me H H H H H Ph Me 21-10 Ph H H H H H H Me 21-11 Ph H H Me H H H Me 21-12 Ph H H H Me H H Me 21-13 Ph H H H H Me H Me 21-14 Ph H H H H H Me Me 21-15 Ph H H Ph H H H Me 21-16 Ph H H H Ph H H Me 21-17 Ph H H H H Ph H Me 21-18 Ph H H H H H Ph Me
21-19 Me Me H H H H H Me 21-20 Me Me H Me H H H Me 21-21 Me Me H H Me H H Me 21-22 Me Me H H H Me H Me 21-23 Me Me H H H H Me Me 21-24 Me Me H Ph H H H Me 21-25 Me Me H H Ph H H Me 21-26 Me Me H H H Ph H Me 21-27 Me Me H H H H Ph Me 21-28 Ph Me H H H H H Me 21-29 Ph Me H Me H H H Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 21-30 Ph Me H H Me H H Me 21-31 Ph Me H H H Me H Me 21-32 Ph Me H H H H Me Me 21-33 Ph Me H Ph H H H Me 21-34 Ph Me H H Ph H H Me 21-35 Ph Me H H H Ph H Me 21-36 Ph Me H H H H Ph Me
21-37 Me H Me H H H H Me 21-38 Me H Me Me H H H Me 21-39 Me H Me H Me H H Me 21-40 Me H Me H H Me H Me 21-41 Me H Me H H H Me Me 21-42 Me H Me Ph H H H Me 21-43 Me H Me H Ph H H Me 21-44 Me H Me H H Ph H Me 21-45 Me H Me H H H Ph Me 21-46 Ph H Me H H H H Me 21-47 Ph H Me Me H H H Me 21-48 Ph H Me H Me H H Me 21-49 Ph H Me H H Me H Me 21-50 Ph H Me H H H Me Me 21-51 Ph H Me Ph H H H Me 21-52 Ph H Me H Ph H H Me 21-53 Ph H Me H H Ph H Me 21-54 Ph H Me H H H Ph Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5
21-55 Me Ph H H H H H Me 21-56 Me Ph H Me H H H Me 21-57 Me Ph H H Me H H Me 21-58 Me Ph H H H Me H Me 21-59 Me Ph H H H H Me Me 21-60 Me Ph H Ph H H H Me 21-61 Me Ph H H Ph H H Me 21-62 Me Ph H H H Ph H Me 21-63 Me Ph H H H H Ph Me 21-64 Ph Ph H H H H H Me 21-65 Ph Ph H Me H H H Me 21-66 Ph Ph H H Me H H Me 21-67 Ph Ph H H H Me H Me 21-68 Ph Ph H H H H Me Me 21-69 Ph Ph H Ph H H H Me 21-70 Ph Ph H H Ph H H Me 21-71 Ph Ph H H H Ph H Me 21-72 Ph Ph H H H H Ph Me
21-73 Me H Ph H H H H Me 21-74 Me H Ph Me H H H Me 21-75 Me H Ph H Me H H Me 21-76 Me H Ph H H Me H Me 21-77 Me H Ph H H H Me Me 21-78 Me H Ph Ph H H H Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 21-79 Me H Ph H Ph H H Me 21-80 Me H Ph H H Ph H Me 21-81 Me H Ph H H H Ph Me 21-82 Ph H Ph H H H H Me 21-83 Ph H Ph Me H H H Me 21-84 Ph H Ph H Me H H Me 21-85 Ph H Ph H H Me H Me 21-86 Ph H Ph H H H Me Me 21-87 Ph H Ph Ph H H H Me 21-88 Ph H Ph H Ph H H Me 21-89 Ph H Ph H H Ph H Me 21-90 Ph H Ph H H H Ph Me
Table 22
Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 22-1 Me H H H H H H H Me 22-2 Me H H H Me H H H Me 22-3 Me H H H H Me H H Me 22-4 Me H H H H H Me H Me 22-5 Me H H H H H H Me Me 22-6 Me H H H Ph H H H Me 22-7 Me H H H H Ph H H Me 22-8 Me H H H H H Ph H Me 22-9 Me H H H H H H Ph Me 22-10 Ph H H H H H H H Me 22-11 Ph H H H Me H H H Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 22-12 Ph H H H H Me H H Me 22-13 Ph H H H H H Me H Me 22-14 Ph H H H H H H Me Me 22-15 Ph H H H Ph H H H Me 22-16 Ph H H H H Ph H H Me 22-17 Ph H H H H H Ph H Me 22-18 Ph H H H H H H Ph Me
22-19 Me Me H H H H H H Me 22-20 Me Me H H Me H H H Me 22-21 Me Me H H H Me H H Me 22-22 Me Me H H H H Me H Me 22-23 Me Me H H H H H Me Me 22-24 Me Me H H Ph H H H Me 22-25 Me Me H H H Ph H H Me 22-26 Me Me H H H H Ph H Me 22-27 Me Me H H H H H Ph Me 22-28 Ph Me H H H H H H Me 22-29 Ph Me H H Me H H H Me 22-30 Ph Me H H H Me H H Me 22-31 Ph Me H H H H Me H Me 22-32 Ph Me H H H H H Me Me 22-33 Ph Me H H Ph H H H Me 22-34 Ph Me H H H Ph H H Me 22-35 Ph Me H H H H Ph H Me 22-36 Ph Me H H H H H Ph Me
22-37 Me H Me H H H H H Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 22-38 Me H Me H Me H H H Me 22-39 Me H Me H H Me H H Me 22-40 Me H Me H H H Me H Me 22-41 Me H Me H H H H Me Me 22-42 Me H Me H Ph H H H Me 22-43 Me H Me H H Ph H H Me 22-44 Me H Me H H H Ph H Me 22-45 Me H Me H H H H Ph Me 22-46 Ph H Me H H H H H Me 22-47 Ph H Me H Me H H H Me 22-48 Ph H Me H H Me H H Me 22-49 Ph H Me H H H Me H Me 22-50 Ph H Me H H H H Me Me 22-51 Ph H Me H Ph H H H Me 22-52 Ph H Me H H Ph H H Me 22-53 Ph H Me H H H Ph H Me 22-54 Ph H Me H H H H Ph Me
22-55 Me H H Me H H H H Me 22-56 Me H H Me Me H H H Me 22-57 Me H H Me H Me H H Me 22-58 Me H H Me H H Me H Me 22-59 Me H H Me H H H Me Me 22-60 Me H H Me Ph H H H Me 22-61 Me H H Me H Ph H H Me 22-62 Me H H Me H H Ph H Me 22-63 Me H H Me H H H Ph Me 22-64 Ph H H Me H H H H Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 22-65 Ph H H Me Me H H H Me 22-66 Ph H H Me H Me H H Me 22-67 Ph H H Me H H Me H Me 22-68 Ph H H Me H H H Me Me 22-69 Ph H H Me Ph H H H Me 22-70 Ph H H Me H Ph H H Me 22-71 Ph H H Me H H Ph H Me 22-72 Ph H H Me H H H Ph Me
22-73 Me Ph H H H H H H Me 22-74 Me Ph H H Me H H H Me 22-75 Me Ph H H H Me H H Me 22-76 Me Ph H H H H Me H Me 22-77 Me Ph H H H H H Me Me 22-78 Me Ph H H Ph H H H Me 22-79 Me Ph H H H Ph H H Me 22-80 Me Ph H H H H Ph H Me 22-81 Me Ph H H H H H Ph Me 22-82 Ph Ph H H H H H H Me 22-83 Ph Ph H H Me H H H Me 22-84 Ph Ph H H H Me H H Me 22-85 Ph Ph H H H H Me H Me 22-86 Ph Ph H H H H H Me Me 22-87 Ph Ph H H Ph H H H Me 22-88 Ph Ph H H H Ph H H Me 22-89 Ph Ph H H H H Ph H Me 22-90 Ph Ph H H H H H Ph Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 22- 91 Me H Ph H H H H H Me 22- 92 Me H Ph H Me H H H Me 22- 93 Me H Ph H H Me H H Me 22- 94 Me H Ph H H H Me H Me 22- 95 Me H Ph H H H H Me Me 22- 96 Me H Ph H Ph H H H Me 22- 97 Me H Ph H H Ph H H Me 22- 98 Me H Ph H H H Ph H Me 22- 99 Me H Ph H H H H Ph Me 22- 100 Ph H Ph H H H H H Me 22- 101 Ph H Ph H Me H H H Me 22- 102 Ph H Ph H H Me H H Me 22- 103 Ph H Ph H H H Me H Me 22- 104 Ph H Ph H H H H Me Me 22- 105 Ph H Ph H Ph H H H Me 22- 106 Ph H Ph H H Ph H H Me 22- 107 Ph H Ph H H H Ph H Me 22- 108 Ph H Ph H H H H Ph Me
22- 109 Me H H Ph H H H H Me 22- 110 Me H H Ph Me H H H Me 22- 111 Me H H Ph H Me H H Me 22- 112 Me H H Ph H H Me H Me 22- 113 Me H H Ph H H H Me Me 22- 114 Me H H Ph Ph H H H Me 22- 115 Me H H Ph H Ph H H Me 22- 116 Me H H Ph H H Ph H Me 22- 117 Me H H Ph H H H Ph Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 22- 118 Ph H H Ph H H H H Me 22- 119 Ph H H Ph Me H H H Me 22- 120 Ph H H Ph H Me H H Me 22- 121 Ph H H Ph H H Me H Me 22- 122 Ph H H Ph H H H Me Me 22- 123 Ph H H Ph Ph H H H Me 22- 124 Ph H H Ph H Ph H H Me 22- 125 Ph H H Ph H H Ph H Me 22- 126 Ph H H Ph H H H Ph Me
Table 23
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 23-1 Me H H H H H H H H Me 23-2 Me H H H H Me H H H Me 23-3 Me H H H H H Me H H Me 23-4 Me H H H H H H Me H Me 23-5 Me H H H H H H H Me Me 23-6 Me H H H H Ph H H H Me 23-7 Me H H H H H Ph H H Me 23-8 Me H H H H H H Ph H Me 23-9 Me H H H H H H H Ph Me 23-10 Ph H H H H H H H H Me 23-11 Ph H H H H Me H H H Me 23-12 Ph H H H H H Me H H Me 23-13 Ph H H H H H H Me H Me 23-14 Ph H H H H H H H Me Me 23-15 Ph H H H H Ph H H H Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 23- 16 Ph H H H H H Ph H H Me 23- 17 Ph H H H H H H Ph H Me 23- 18 Ph H H H H H H H Ph Me
23- 19 Me Me H H H H H H H Me 23-20 Me Me H H H Me H H H Me 23-21 Me Me H H H H Me H H Me 23-22 Me Me H H H H H Me H Me 23-23 Me Me H H H H H H Me Me 23-24 Me Me H H H Ph H H H Me 23-25 Me Me H H H H Ph H H Me 23-26 Me Me H H H H H Ph H Me 23-27 Me Me H H H H H H Ph Me 23-28 Ph Me H H H H H H H Me 23-29 Ph Me H H H Me H H H Me 23-30 Ph Me H H H H Me H H Me 23-31 Ph Me H H H H H Me H Me 23-32 Ph Me H H H H H H Me Me 23-33 Ph Me H H H Ph H H H Me 23-34 Ph Me H H H H Ph H H Me 23-35 Ph Me H H H H H Ph H Me 23-36 Ph Me H H H H H H Ph Me
23-37 Me H Me H H H H H H Me 23-38 Me H Me H H Me H H H Me 23-39 Me H Me H H H Me H H Me 23-40 Me H Me H H H H Me H Me 23-41 Me H Me H H H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 23-42 Me H Me H H Ph H H H Me 23-43 Me H Me H H H Ph H H Me 23-44 Me H Me H H H H Ph H Me 23-45 Me H Me H H H H H Ph Me 23-46 Ph H Me H H H H H H Me 23-47 Ph H Me H H Me H H H Me 23-48 Ph H Me H H H Me H H Me 23-49 Ph H Me H H H H Me H Me 23-50 Ph H Me H H H H H Me Me 23-51 Ph H Me H H Ph H H H Me 23-52 Ph H Me H H H Ph H H Me 23-53 Ph H Me H H H H Ph H Me 23-54 Ph H Me H H H H H Ph Me
23-55 Me H H Me H H H H H Me 23-56 Me H H Me H Me H H H Me 23-57 Me H H Me H H Me H H Me 23-58 Me H H Me H H H Me H Me 23-59 Me H H Me H H H H Me Me 23-60 Me H H Me H Ph H H H Me 23-61 Me H H Me H H Ph H H Me 23-62 Me H H Me H H H Ph H Me 23-63 Me H H Me H H H H Ph Me 23-64 Ph H H Me H H H H H Me 23-65 Ph H H Me H Me H H H Me 23-66 Ph H H Me H H Me H H Me 23-67 Ph H H Me H H H Me H Me 23-68 Ph H H Me H H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 RbS 23-69 Ph H H Me H Ph H H H Me 23-70 Ph H H Me H H Ph H H Me 23-71 Ph H H Me H H H Ph H Me 23-72 Ph H H Me H H H H Ph Me
23-73 Me H H H Me H H H H Me 23-74 Me H H H Me Me H H H Me 23-75 Me H H H Me H Me H H Me 23-76 Me H H H Me H H Me H Me 23-77 Me H H H Me H H H Me Me 23-78 Me H H H Me Ph H H H Me 23-79 Me H H H Me H Ph H H Me 23-80 Me H H H Me H H Ph H Me 23-81 Me H H H Me H H H Ph Me 23-82 Ph H H H Me H H H H Me 23-83 Ph H H H Me Me H H H Me 23-84 Ph H H H Me H Me H H Me 23-85 Ph H H H Me H H Me H Me 23-86 Ph H H H Me H H H Me Me 23-87 Ph H H H Me Ph H H H Me 23-88 Ph H H H Me H Ph H H Me 23-89 Ph H H H Me H H Ph H Me 23-90 Ph H H H Me H H H Ph Me
23-91 Me Ph H H H H H H H Me 23-92 Me Ph H H H Me H H H Me 23-93 Me Ph H H H H Me H H Me 23-94 Me Ph H H H H H Me H Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 23- 95 Me Ph H H H H H H Me Me 23- 96 Me Ph H H H Ph H H H Me 23- 97 Me Ph H H H H Ph H H Me 23- 98 Me Ph H H H H H Ph H Me 23- 99 Me Ph H H H H H • H Ph Me 23- 100 Ph Ph H H H H H H H Me 23- 101 Ph Ph H H H Me H H H Me 23- 102 Ph Ph H H H H Me H H Me 23- 103 Ph Ph H H H H H Me H Me 23- 104 Ph Ph H H H H H H Me Me 23- 105 Ph Ph H H H Ph H H H Me 23- 106 Ph Ph H H H H Ph H H Me 23- 107 Ph Ph H H H H H Ph H Me 23- 108 Ph Ph H H H H H H Ph Me
23- 109 Me H Ph H H H H H H Me 23- 110 Me H Ph H H Me H H H Me 23- 111 Me H Ph H H H Me H H Me 23- 112 Me H Ph H H H H Me H . Me 23- 113 Me H Ph H H H H H Me Me 23- 114 Me H Ph H H Ph H H H Me 23- 115 Me H Ph H H H Ph H H Me 23- 116 Me H Ph H H H H Ph H Me 23- 117 Me H Ph H H H H H Ph Me 23- 118 Ph H Ph H H H H H H Me 23- 119 Ph H Ph H H Me H H H Me 23- 120 Ph H Ph H H H Me H H Me 23- 121 Ph H Ph H H H H Me H Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 23- 122 Ph H Ph H H H H H Me Me 23- 123 Ph H Ph H H Ph H H H Me 23- 124 Ph H Ph H H H Ph H H Me 23- 125 Ph H Ph H H H H Ph H Me 23- 126 Ph H Ph H H H H H Ph Me
23- 127 Me H H Ph H H H H H Me 23- 128 Me H H Ph H Me H H H Me 23- 129 Me H H Ph H H Me H H Me 23- 130 Me H H Ph H H H Me H Me 23- 131 Me H H Ph H H H H Me Me 23- 132 Me H H Ph H Ph H H H Me 23- 133 Me H H Ph H H Ph H H Me 23- 134 Me H H Ph H H H Ph H Me 23- 135 Me H H Ph H H H H Ph Me 23- 136 Ph H H Ph H H H H H Me 23- 137 Ph H H Ph H Me H H H Me 23- 138 Ph H H Ph H H Me H H Me 23- 139 Ph H H Ph H H H Me H Me 23- 140 Ph H H Ph H H H H Me Me 23- 141 Ph H H Ph H Ph H H H Me 23- 142 Ph H H Ph H H Ph H H Me 23- 143 Ph H H Ph H H H Ph H Me 23- 144 Ph H H Ph H H H H Ph Me
23- 145 Me H H H Ph H H H H Me 23- 146 Me H H H Ph Me H H H . Me 23- 147 Me H H H Ph H Me H H Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 Rb5 23- 148 Me H H H Ph H H Me H Me 23- 149 Me H H H Ph H H H Me Me 23- 150 Me H H H Ph Ph H H H Me 23- 151 Me H H H Ph H Ph H H Me 23- 152 Me H H H Ph H H Ph H Me 23- 153 Me H H H Ph H H H Ph Me 23- 154 Ph H H H Ph H H H H Me 23- 155 Ph H H H Ph Me H H H Me 23- 156 Ph H H H Ph H Me H H Me 23- 157 Ph H H H Ph H H Me H Me 23- 158 Ph H H H Ph H H H Me Me 23- 159 Ph H H H Ph Ph H H H Me 23- 160 Ph H H H Ph H Ph H H Me 23- 161 Ph H H H Ph H H Ph H Me 23- 162 Ph H H H Ph H H H Ph Me
Table 24
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra' r Rbl Rb2 Rb3 Rb4 Rb5 24- 1 Me H H H H H H H H H H Me 24- 2 Me H H H H H H Me H H H Me 24- 3 Me H H H H H H H Me H H Me 24- 4 Me H H H H H H H H Me H Me 24- 5 Me H H H H H H H H . H Me Me 24- 6 Me H H H H H H Ph H H H Me 24- 7 Me H H H H H H H Ph H H Me 24- 8 Me H H H H H H H H Ph H Me 24- 9 Me H H H H H H H H H Ph Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 24- 10 Ph H H H H H H H H H H Me 24- 11 Ph H H H H H H Me H H H Me 24- 12 Ph H H H H H H H Me H H Me 24- 13 Ph H H H H H H H H Me H Me 24- 14 Ph H H H H H H H H H Me Me 24- 15 Ph H H H H H H Ph H H H Me 24- 16 Ph H H H H H H H Ph H H Me 24- 17 Ph H H H H H H H H Ph H Me 24- 18 Ph H H H H H H H H H Ph Me
24- 19 Me Me H H H H H H H H H Me 24-20 Me Me H H H H H Me H H H Me 24-21 Me Me H H H H H H Me H H Me 24-22 Me Me H H H H H H H Me H Me 24-23 Me Me H H H H H H H H Me Me 24-24 Me Me H H H H H Ph H H H Me 24-25 Me Me H H H H H H Ph H H Me 24-26 Me Me H " H H H H H H Ph H Me 24-27 Me Me H H H H H H H H Ph Me 24-28 Ph Me H H H H H H H H H Me 24-29 Ph Me H H H H H Me H H H Me 24-30 Ph Me H H H H H H Me H H Me 24-31 Ph Me H H H H H H H Me H Me 24-32 Ph Me H H H H H H H H Me Me 24-33 Ph Me H H H H H Ph H H H Me 24-34 Ph Me H H H H H H Ph H H Me 24-35 Ph Me H H H H H H H Ph H Me 24-36 Ph Me H H H H H H H H Ph Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5
24-37 Me H Me H H H H H H H H Me 24-38 Me H Me H H H H Me H H H Me 24-39 Me H Me H H H H H Me H H Me 24-40 Me H Me H H H H H H Me H Me 24-41 Me H Me H H H H H H H Me Me 24-42 Me H Me H H H H Ph H H H Me 24-43 Me H Me H H H H H Ph H H Me 24-44 Me H Me H H H H H H Ph H Me 24-45 Me H Me H H H H H H H Ph Me 24-46 Ph H Me H H H H H H H H Me 24-47 Ph H Me H H H H Me H H H Me 24-48 Ph H Me H H H H H Me H H Me 24-49 Ph H Me H H H H H H Me H Me 24-50 Ph H Me H H H H H H H Me Me 24-51 Ph H Me H H H H Ph H H H Me 24-52 Ph H Me H H H H H Ph H H Me 24-53 Ph H Me H H H H H H Ph H Me 24-54 Ph H Me H H H H H H H Ph Me
24-55 Me H H Me H H H H H H H Me 24-56 Me H H Me H H H Me H H H Me 24-57 Me H H Me H H H H Me H H Me 24-58 Me H H Me H H H H H Me H Me 24-59 Me H H Me H H H H H H Me Me 24-60 Me H H Me H H H Ph H H H Me 24-61 Me H H Me H H H H Ph H H Me 24-62 Me H H Me H H H H H Ph H Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 24-63 Me H H Me H H H H H H Ph Me 24-64 Ph H H Me H H H H H H H Me 24-65 Ph H H Me H H H Me H H H Me 24-66 Ph H H Me H H H H Me H H Me 24-67 Ph H H Me H H H H H Me H Me 24-68 Ph H H Me H H H H H H Me Me 24-69 Ph H H Me H H H Ph H H H Me 24-70 Ph H H Me H H H H Ph H H Me 24-71 Ph H H Me H H H H H Ph H Me 24-72 Ph H H Me H H H H H H Ph Me
24-73 Me H H H Me H H H H H H Me 24-74 Me H H H Me H H Me H H H Me 24-75 Me H H H Me H H H Me H H Me 24-76 Me H H H Me H H H H Me H Me 24-77 Me H H H Me H H H H H Me Me 24-78 Me H H H Me H H Ph H H H Me 24-79 Me H H H Me H H H Ph H H Me 24-80 Me H H H Me H H H H Ph H Me 24-81 Me H H H Me H H H H H Ph Me 24-82 Ph H H H Me H H H H H H Me 24-83 Ph H H H Me H H Me H H H Me 24-84 Ph H H H Me H H H Me H H Me 24-85 Ph H H H Me H H H H Me H Me 24-86 Ph H H H Me H H H H H Me Me 24-87 Ph H H H Me H H Ph H H H Me 24-88 Ph H H H Me H H H Ph H H Me 24-89 Ph H H H Me H H H H Ph H Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 24- 90 Ph H H H Me H H H H H Ph Me
24- 91 Me H H H H Me H H H H H Me 24- 92 Me H H H H Me H Me H H H Me 24- 93 Me H H H H Me H H Me H H Me 24- 94 Me H H H H Me H H H Me H Me 24- 95 Me H H H H Me H H H H Me Me 24- 96 Me H H H H Me H Ph H H H . Me 24- 97 Me H H H H Me H H Ph H H Me 24- 98 Me H H H H Me H H H Ph H Me 24- 99 Me H H H H Me H H H H Ph Me 24- 100 Ph H H H H Me H H H H H Me 24- 101 Ph H H H H Me H Me H H H Me 24- 102 Ph H H H H Me H H Me H H Me 24- 103 Ph H H H H Me H H H Me H Me 24- 104 Ph H H H H Me H H H H Me Me 24- 105 Ph H H H H Me H Ph H H H Me 24- 106 Ph H H H H Me H H Ph H H Me 24- 107 Ph H H H H Me H H H Ph H Me 24- 108 Ph H H H H Me H H H H Ph Me
24- 109 Me H H H H H Me H H H H Me 24- 110 Me H H H H H Me Me H H H Me 24- 111 Me H H H H H Me H Me H H Me 24- 112 Me H H H H H Me H H Me H Me 24- 113 Me H H H H H Me H H H Me Me 24- 114 Me H H H H H Me Ph H H H Me 24- 115 Me H H H H H Me H Ph H H Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 24- 116 Me H H H H H Me H H Ph H Me 24- 117 Me H H H H H Me H H H Ph Me 24- 118 Ph H H H H H Me H H H H Me 24- 119 Ph H H H H H Me Me H H H Me 24- 120 Ph H H H H H Me H Me H H Me 24- 121 Ph H H H H H Me H H Me H Me 24- 122 Ph H H H H H Me H H H Me Me 24- 123 Ph H H H H H Me Ph H H H Me 24- 124 Ph H H H H H Me H Ph H H Me 24- 125 Ph H H H H H Me H H Ph H Me 24- 126 Ph H H H H H Me H H H Ph Me
24- 127 Me Ph H H H H H H H H H Me 24- 128 Me Ph H H H H H Me H H H Me 24- 129 Me Ph H H H H H H Me H H Me 24- 130 Me Ph H H H H H H H Me H Me 24- 131 Me Ph H H H H H H H H Me Me 24- 132 Me Ph H H H H H Ph H H H Me 24- 133 Me Ph H H H H H H Ph H H Me 24- 134 Me Ph H H H H H H H Ph H Me 24- 135 Me Ph H H H H H H H H Ph Me 24- 136 Ph Ph H H H H H H H H H Me 24- 137 Ph Ph H H H H H Me H H H Me 24- 138 Ph Ph H H H H H H Me H H Me 24- 139 Ph Ph H H H H H H H Me H Me 24- 140 Ph Ph H H H H H H H H Me Me 24- 141 Ph Ph H H H H H Ph H H H Me 24- 142 Ph Ph H H H H H H Ph H H Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 24- 143 Ph Ph H H H H H H H Ph H Me 24- 144 Ph Ph H H H H H H H H Ph Me
24- 145 Me H Ph H H H H H H H H Me 24- 146 Me H Ph H H H H Me H H H Me 24- 147 Me H Ph H H H H H Me H H Me 24- 148 Me H Ph H H H H H H Me H Me 24- 149 Me H Ph H H H H H H H Me Me 24- 150 Me H Ph H H H H Ph H H H Me 24- 151 Me H Ph H H H H H Ph H H Me 24- 152 Me H Ph H H H H H H Ph H Me 24- 153 Me H Ph H H H H H H H Ph Me 24- 154 Ph H Ph H H H H H H H H Me 24- 155 Ph H Ph H H H H Me H H H Me 24- 156 Ph H Ph H H H H H Me H H Me 24- 157 Ph H Ph H H H H H H Me H Me 24- 158 Ph H Ph H H H H H H H Me Me 24- 159 Ph H Ph H H H H Ph H H H Me 24- 160 Ph H Ph H H H H H Ph H H Me 24- 161 Ph H Ph H H H H H H Ph H Me 24- 162 Ph H Ph H H H H H H H Ph Me
24- 163 Me H H Ph H H H H H H H Me 24- 164 Me H ( H Ph H H H Me H H H Me 24- 165 Me H H Ph H H H H Me H H Me 24- 166 Me H H Ph H H H H H Me H Me 24- 167 Me H H Ph H H H H H H Me Me 24- 168 Me H H Ph H H H Ph H H H Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 24- 169 Me H H Ph H H H H Ph H H Me 24- 170 Me H H Ph H H H H H Ph H Me 24- 171 Me H H Ph H H H H H H Ph Me 24- 172 Ph H H Ph H H H H H H H Me 24- 173 Ph H H Ph H H H Me H H H Me 24- 174 Ph H H Ph H H H H Me H H Me 24- 175 Ph H H Ph H H H H H Me H Me 24- 176 Ph H H Ph H H H H H H Me Me 24- 177 Ph H H Ph H H H Ph H H H Me 24- 178 Ph H H Ph H H H H Ph H H Me 24- 179 Ph H H Ph H H H H H Ph H Me 24- 180 Ph H H Ph H H H H H H Ph Me
24- 181 Me H H H Ph H H H H H H Me 24- 182 Me H H H Ph H H Me H H H Me 24- 183 Me H H H Ph H H H Me H H Me 24- 184 Me H H H Ph H H H H Me H Me 24- 185 Me H H H Ph H H H H H Me Me 24- 186 Me H H H Ph H H Ph H H H Me 24- 187 Me H H H Ph H H H Ph H H Me 24- 188 Me H H H Ph H H H H Ph H Me 24- 189 Me H H H Ph H H H H H Ph Me 24- 190 Ph H H H Ph H H H H H H Me 24- 191 Ph H H H Ph H H Me H H H Me 24- 192 Ph H H H Ph H H H Me H H Me 24- 193 Ph H H H Ph H H H H Me H Me 24- 194 Ph H H H Ph H H H H H Me Me 24- 195 Ph H H H Ph H H Ph H H H Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 24- 196 Ph H H H Ph H H H Ph H H Me 24- 197 Ph H H H Ph H H H H Ph H Me 24- 198 Ph H H H Ph H H H H H Ph Me
24- 199 Me H H H H Ph H H H H H Me 24- 200 Me H H H H Ph H Me H H H Me 24- 201 Me H H H H Ph H H Me H H Me 24- 202 Me H H H H Ph H H H Me H Me 24- 203 Me H H H H Ph H H H H Me Me 24- 204 Me H H H H Ph H Ph H H H Me 24- 205 Me H H H H Ph H H Ph H H Me 24- 206 Me H H H H Ph H H H Ph H Me 24- 207 Me H H H H Ph H H H H Ph Me 24- 208 Ph H H H H Ph H H H H H Me 24- 209 Ph H H H H Ph H Me H H H Me 24- 210 Ph H H H H Ph H H Me H H Me 24- 211 Ph H H H H Ph H H H Me H Me 24- 212 Ph H H H H Ph H H H H Me Me 24- 213 Ph H H H H Ph H Ph H H H Me 24- 214 Ph H H H H Ph H H Ph H H Me 24- 215 Ph H H H H Ph H H H Ph H Me 24- 216 Ph H H H H Ph H H H H Ph Me
24- 217 Me H H H H H Ph H H H H Me 24- 218 Me H H H H H Ph Me H H H Me 24- 219 Me H H H H H Ph H Me H H Me 24- 220 Me H H H H H Ph H H Me H Me 24- 221 Me H H H H H Ph H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 24- 222 Me H H H H H Ph Ph H H H Me 24- 223 Me H H H H H Ph H Ph H H Me 24- 224 Me H H H H H Ph H H Ph H Me 24- 225 Me H H H H H Ph H H H Ph Me 24- 226 Ph H H H H H Ph H H H H Me 24- 227 Ph H H H H H Ph Me H H H Me 24- 228 Ph H H H H H Ph H Me H H Me 24- 229 Ph H H H H H Ph H H Me H Me 24- 230 Ph H H H H H Ph H H H Me Me 24- 231 Ph H H H H H Ph Ph H H H Me 24- 232 Ph H H H H H Ph H Ph H H Me 24- 233 Ph H H H H H Ph H H Ph H Me 24- 234 Ph H H H H H Ph H H H Ph Me
Table 25
Cpd No. Rai Ra2 Ra3 Rbl Rb2 25- 1 Me Me Me H H 25- 2 Me Me Me Me H 25- 3 Me Me Me H Me 25- 4 Me Me Me Ph H 25- 5 Me Me Me H Ph 25- 6 Ph Me Me H H 25- 7 Ph Me Me Me H 25- 8 Ph Me Me H Me 25- 9 Ph Me Me Ph H 25- 10 Ph Me Me H Ph Cpd No. Rai Ra2 Ra3 Rbl Rb2 25- 11 Me Ph Me H H 25-12 Me Ph Me Me H 25-13 Me Ph Me H Me 25-14 Me Ph Me Ph H 25- 15 Me Ph Me H Ph 25- 16 Ph Ph Me H H 25- 17 Ph Ph Me Me H 25-18 Ph Ph Me H Me 25- 19 Ph Ph Me Ph H 25-20 Ph Ph Me H Ph
25-21 Me Me Ph H H 25-22 Me Me Ph Me H 25-23 Me Me Ph H Me 25-24 Me Me Ph Ph H 25-25 Me Me Ph H Ph 25-26 Ph Me Ph H H 25-27 Ph Me Ph Me H 25-28 Ph Me Ph H Me 25-29 Ph Me Ph Ph H 25-30 Ph Me Ph H Ph
25-31 Me Ph Ph H H 25-32 Me Ph Ph Me H 25-33 Me Ph Ph H Me 25-34 Me Ph Ph Ph H 25-35 Me Ph Ph H Ph 25-36 Ph Ph Ph H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 25-37 Ph Ph Ph Me H 25-38 Ph Ph Ph H Me 25-39 Ph Ph Ph Ph H 25-40 Ph Ph Ph H Ph
Table 26
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 26-1 Me Me Me H H H H 26-2 Me Me Me Me H H H 26-3 Me Me Me H Me H H 26-4 Me Me Me H H Me H 26-5 Me Me Me H H H Me 26-6 Me Me Me Ph H H H 26-7 Me Me Me H Ph H H 26-8 Me Me Me H H Ph H 26-9 Me Me Me H H H Ph 26-10 Ph Me Me H H H H 26-11 Ph Me Me Me H H H 26- 12 Ph Me Me H Me H H 26- 13 Ph Me Me H H Me H 26-14 Ph Me Me H H H Me 26- 15 Ph Me Me Ph H H H 26-16 Ph Me Me H Ph H H 26-17 Ph Me Me H H Ph H 26- 18 Ph Me Me H H H Ph
26-19 Me Ph Me H H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 26-20 Me Ph Me Me H H H 26-21 Me Ph Me H Me H H 26-22 Me Ph Me H H Me H 26-23 Me Ph Me H H H Me 26-24 Me Ph Me Ph H H H 26-25 Me Ph Me H Ph H H 26-26 Me Ph Me H H Ph H 26-27 Me Ph Me H H H Ph 26-28 Ph Ph Me H H H H 26-29 Ph Ph Me Me H H H 26-30 Ph Ph Me H Me H H 26-31 Ph Ph Me H H Me H 26-32 Ph Ph Me H H H Me 26-33 Ph Ph Me Ph H H H 26-34 Ph Ph Me H Ph H H 26-35 Ph Ph Me H H Ph H 26-36 Ph Ph Me H H H Ph
26-37 Me Me Ph H H H H 26-38 Me Me Ph Me H H H 26-39 Me Me Ph H Me H H 26-40 Me Me Ph H H Me H 26-41 Me Me Ph H H H Me 26-42 Me Me Ph Ph H H H 26-43 Me Me Ph H Ph H H 26-44 Me Me Ph H H Ph H 26-45 Me Me Ph H H H Ph 26-46 Ph Me Ph H H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 26-47 Ph Me Ph Me H H H 26-48 Ph Me Ph H Me H H 26-49 Ph Me Ph H H Me H 26-50 Ph Me Ph H H H Me 26-51 Ph Me Ph Ph H H H 26-52 Ph Me Ph H Ph H H 26-53 Ph Me Ph H H Ph H 26-54 Ph Me Ph H H H Ph
26-55 Me Ph Ph H H H H 26-56 Me Ph Ph Me H H H 26-57 . Me Ph Ph H Me H H 26-58 Me Ph Ph H H Me H 26-59 Me Ph Ph H H H Me 26-60 Me Ph Ph Ph H H H 26-61 Me Ph Ph H Ph H H 26-62 Me Ph Ph H H Ph H 26-63 Me Ph Ph H H H Ph 26-64 Ph Ph Ph H H H H 26-65 Ph Ph Ph Me H H H 26-66 Ph Ph Ph H Me H H 26-67 Ph Ph Ph H H Me H 26-68 Ph Ph Ph H H H Me 26-69 Ph Ph Ph Ph H H H 26-70 Ph Ph Ph H Ph H H 26-71 Ph Ph Ph H H Ph H 26-72 Ph Ph Ph H H H Ph Table 27
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 27-1 Me Me Me H H H H Me 27-2 Me Me Me Me H H H Me 27-3 Me Me Me H Me H H Me 27-4 Me Me Me H H Me H Me 27-5 Me Me Me H H H Me Me 27-6 Me Me Me Ph H H H Me 27-7 Me Me Me H Ph H H Me 27-8 Me Me Me H H Ph H Me 27-9 Me Me Me H H H Ph Me 27-10 Ph Me Me H H H H Me 27-11 Ph Me Me Me H H H Me 27- 12 Ph Me Me H Me H H Me 27- 13 Ph Me Me H H Me H Me 27- 14 Ph Me Me H H H Me Me 27-15 Ph Me Me Ph H H H Me 27-16 Ph Me Me H Ph H H Me 27- 17 Ph Me Me H H Ph H Me 27- 18 Ph Me Me H H H Ph Me
27- 19 Me Ph Me H H H H Me 27-20 Me Ph Me Me H H H Me 27-21 Me Ph Me H Me H H Me 27-22 Me Ph Me H H Me H Me 27-23 Me Ph Me H H H Me Me 27-24 Me Ph Me Ph H H H Me 27-25 Me Ph Me H Ph H H Me 27-26 Me Ph Me H H Ph H Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 RbS 27-27 Me Ph Me H H H Ph Me 27-28 Ph Ph Me H H H H Me 27-29 Ph Ph Me Me H H H Me 27-30 Ph Ph Me H Me H H Me 27-31 Ph Ph Me H H Me H Me 27-32 Ph Ph Me H H H Me Me 27-33 Ph Ph Me Ph H H H Me 27-34 Ph Ph Me H Ph H H Me 27-35 Ph Ph Me H H Ph H Me 27-36 Ph Ph Me H H H Ph Me
27-37 Me Me Ph H H H H Me 27-38 Me Me Ph Me H H H Me 27-39 Me Me Ph H Me H H Me 27-40 Me Me Ph H H Me H Me 27-41 Me Me Ph H H H Me Me 27-42 Me Me Ph Ph H H H Me 27-43 Me Me Ph H Ph H H Me 27-44 Me Me Ph H H Ph H Me 27-45 Me Me Ph H H H Ph Me 27-46 Ph Me Ph H H H H Me 27-47 Ph Me Ph Me H H H Me 27-48 Ph Me Ph H Me H H Me 27-49 Ph Me Ph H H Me H Me 27-50 Ph Me Ph H H H Me Me 27-51 Ph Me Ph Ph H H H Me 27-52 Ph Me Ph H Ph H H Me 27-53 Ph Me Ph H H Ph H Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 27-54 Ph Me Ph H H H Ph Me
27-55 Me Ph Ph H H H H Me 27-56 Me Ph Ph Me H H H Me 27-57 Me Ph Ph H Me H H Me 27-58 Me Ph Ph H H Me H Me 27-59 Me Ph Ph H H H Me Me 27-60 Me Ph Ph Ph H H H Me 27-61 Me Ph Ph H Ph H H Me 27-62 Me Ph Ph H H Ph H Me 27-63 Me Ph Ph H H H Ph Me 27-64 Ph Ph Ph H H H H Me 27-65 Ph Ph Ph Me H H H Me 27-66 Ph Ph Ph H Me H H Me 27-67 Ph Ph Ph H H Me H Me 27-68 Ph Ph Ph H H H Me Me 27-69 Ph Ph Ph Ph H H H Me 27-70 Ph Ph Ph H Ph H H Me 27-71 Ph Ph Ph H H Ph H Me 27-72 Ph Ph Ph H H H Ph Me
Table 28
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 28-1 Me Me Me H H H H H H 28-2 Me Me Me Me H H H H H 28-3 Me Me Me H Me H H H H 28-4 Me Me Me H H Me H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 28-5 Me Me Me H H H Me H H 28-6 Me Me Me H H H H Me H 28-7 Me Me Me H H H H H Me 28-8 Me Me Me Ph H H H H H 28-9 Me Me Me H Ph H H H H 28-10 Me Me Me H H Ph H H H 28-11 Me Me Me H H H Ph H H 28- 12 Me Me Me H H H H Ph H 28-13 Me Me Me H H H H H Ph 28- 14 Ph Me Me H H H H H H 28- 15 Ph Me Me Me H H H H H 28-16 Ph Me Me H Me H H H H 28- 17 Ph Me Me H H Me H H H 28- 18 Ph Me Me H H H Me H H 28-19 Ph Me Me H H H H Me H 28-20 Ph Me Me H H H H H Me 28-21 Ph Me Me Ph H H H H H 28-22 Ph Me Me H Ph H H H H 28-23 Ph Me Me H H Ph H H H 28-24 Ph Me Me H H H Ph H H 28-25 Ph Me Me H H H H Ph H 28-26 Ph Me Me H H H H H Ph
28-27 Me Ph Me H H H H H H 28-28 Me Ph Me Me H H H H H 28-29 Me Ph Me H Me H H H H 28-30 Me Ph Me H H Me H H H 28-31 Me Ph Me H H H Me H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 28-32 Me Ph Me H H H H Me H 28-33 Me Ph Me H H H H H Me 28-34 Me Ph Me Ph H H H H H 28-35 Me Ph Me H Ph H H H H 28-36 Me Ph Me H H Ph H H H 28-37 Me Ph Me H H H Ph H H 28-38 Me Ph Me H H H H Ph H 28-39 Me Ph Me H H H H H Ph 28-40 Ph Ph Me H H H H H H 28-41 Ph Ph Me Me H H H H H 28-42 Ph Ph Me H Me H H H H 28-43 Ph Ph Me H H Me H H H 28-44 Ph Ph Me H H H Me H H 28-45 Ph Ph Me H H H H Me H 28-46 Ph Ph Me H H H H H Me 28-47 Ph Ph Me Ph H H H H H 28-48 Ph Ph Me H Ph H H H H 28-49 Ph Ph Me H H Ph H H H 28-50 Ph Ph Me H . H H Ph H H 28-51 Ph Ph Me H H H H Ph H 28-52 Ph Ph Me H H H H H Ph
28-53 Me Me Ph H H H H H H 28-54 Me Me Ph Me H H H H H 28-55 Me Me Ph H Me H H H H 28-56 Me Me Ph H H Me H H H 28-57 Me Me Ph H H H Me H H 28-58 Me Me Ph H H H H Me H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 28-59 Me Me Ph H H H H H Me 28-60 Me Me Ph Ph H H H H H 28-61 Me Me Ph H Ph H H H H 28-62 Me Me Ph H H Ph H H H 28-63 Me Me Ph H H H Ph H H 28-64 Me Me Ph H H H H Ph H 28-65 Me Me Ph H H H H H Ph 28-66 Ph Me Ph H H H H H H 28-67 Ph Me Ph Me H H H H H 28-68 Ph Me Ph H Me H H H H 28-69 Ph Me Ph H H Me H H H 28-70 Ph Me Ph H H H Me H H 28-71 Ph Me Ph H H H H Me H 28-72 Ph Me Ph H H H H H Me 28-73 Ph Me Ph Ph H H H H H 28-74 Ph Me Ph H Ph H H H H 28-75 Ph Me Ph H H Ph H H H 28-76 Ph Me Ph H H H Ph H H 28-77 Ph Me Ph H H H H Ph H 28-78 Ph Me Ph H H H H H Ph
28-79 Me Ph Ph H H H H H H 28-80 Me Ph Ph Me H H H H H 28-81 Me Ph Ph H Me H H H H 28-82 Me Ph Ph H H Me H H H 28-83 Me Ph Ph H H H Me H H 28-84 Me Ph Ph H H H H Me H 28-85 Me Ph Ph H H H H H Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 28-86 Me Ph Ph Ph H H H H H 28-87 Me Ph Ph H Ph H H H H 28-88 Me Ph Ph H H Ph H H H 28-89 Me Ph Ph H H H Ph H H 28-90 Me Ph Ph H H H H Ph H 28-91 Me Ph Ph H H H H H Ph 28-92 Ph Ph Ph H H H H H H 28-93 Ph Ph Ph Me H H H H H 28-94 Ph Ph Ph H Me H H H H 28-95 Ph Ph Ph H H Me H H H 28-96 Ph Ph Ph H H H Me H H 28-97 Ph Ph Ph H H H H Me H 28-98 Ph Ph Ph H H H H H Me 28-99 Ph Ph Ph Ph H H H H H 28- 100 Ph Ph Ph H Ph H H H H 28- 101 Ph Ph Ph H H Ph H H H 28- 102 Ph Ph Ph H H H Ph H H 28- 103 Ph Ph Ph H H H H Ph H 28- 104 Ph Ph Ph H H H H H Ph
Table 29
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 29- 1 Me Me Me H H H H H H H 29-2 Me Me Me Me H H H H H H 29-3 Me Me Me H Me H H H H H 29-4 Me Me Me H H Me H H H H 29-5 Me Me Me H H H Me H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 29-6 Me Me Me H H H H Me H H 29-7 Me Me Me H H H H H Me H 29-8 Me Me Me H H H H H H Me 29-9 Me Me Me Ph H H H H H H 29-10 Me Me Me H Ph H H H H H 29-11 Me Me Me H H Ph H H H H 29-12 Me Me Me H H H Ph H H H 29- 13 Me Me Me H H H H Ph H H 29-14 Me Me Me H H H H H Ph H 29-15 Ph Me Me H H H H H H Ph 29-16 Ph Me Me H H H H H H H 29- 17 Ph Me Me Me H H H H H H 29- 18 Ph Me Me H Me H H H H H 29- 19 Ph Me Me H H Me H H H H 29-20 Ph Me Me H H H Me H H H 29-21 Ph Me Me H H H H Me H H 29-22 Ph Me Me H H H H H Me H 29-23 Ph Me Me H H H H H H Me 29-24 Ph Me Me Ph H H H H H H 29-25 Ph Me Me H Ph H H H H H 29-26 Ph Me Me H H Ph H H H H 29-27 Ph Me Me H H H Ph H H H 29-28 Ph Me Me H H H H Ph H H 29-29 Ph Me Me H H H H H Ph H 29-30 Ph Me Me H H H H H H Ph
29-31 Me Ph Me H H H H H H H 29-32 Me Ph Me Me H H H H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 29-33 Me Ph Me H Me H H H H H 29-34 Me Ph Me H H Me H H H H 29-35 Me Ph Me H H H Me H H H 29-36 Me Ph Me H H H H Me H H 29-37 Me Ph Me H H H H H Me H 29-38 Me Ph Me H H H H H H Me 29-39 Me Ph Me Ph H H H H H H 29-40 Me Ph Me H Ph H H H H H 29-41 Me Ph Me H H Ph H H H H 29-42 Me Ph Me H H H Ph H H H 29-43 Me Ph Me H H H H Ph H H 29-44 Me Ph Me H H H H H Ph H 29-45 Ph Ph Me H H H H H H Ph 29-46 Ph Ph Me H H H H H H H 29-47 Ph Ph Me Me H H H H H H 29-48 Ph Ph Me H Me H H H H H 29-49 Ph Ph Me H H Me H H H H 29-50 Ph Ph Me H H H Me H H H 29-51 Ph Ph Me H H H H Me H H 29-52 Ph Ph Me H H H H H Me H 29-53 Ph Ph Me H H H H H H Me 29-54 Ph Ph Me Ph H H H H H H 29-55 Ph Ph Me H Ph H H H H H 29-56 Ph Ph Me H H Ph H H H H 29-57 Ph Ph Me H H H Ph H H H 29-58 Ph Ph Me H H H H Ph H H 29-59 Ph Ph Me H H H H H Ph H 29-60 Ph Ph Me H H H H H H Ph Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7
29-61 Me Me Ph H H H H H H H 29-62 Me Me Ph Me H H H H H H 29-63 Me Me Ph H Me H H H H H 29-64 Me Me Ph H H Me H H H H 29-65 Me Me Ph H H H Me H H H 29-66 Me Me Ph H H H H Me H H 29-67 Me Me Ph H H H H H Me H 29-68 Me Me Ph H H H H H H Me 29-69 Me Me Ph Ph H H H H H H 29-70 Me Me Ph H Ph H H H H H 29-71 Me Me Ph H H Ph H H H H 29-72 Me Me Ph H H H Ph H H H 29-73 Me Me Ph H H H H Ph H H 29-74 Me Me Ph H H H H H Ph H 29-75 Ph Me Ph H H H H H H Ph 29-76 Ph Me Ph H H H H H H H 29-77 Ph Me Ph Me H H H H H H 29-78 Ph Me Ph H Me H H H H H 29-79 Ph Me Ph H H Me H H H H 29-80 Ph Me Ph H H H Me H H H 29-81 Ph Me Ph H H H H Me H H 29-82 Ph Me Ph H H H H H Me H 29-83 Ph Me Ph H H H H H H Me 29-84 Ph Me Ph Ph H H H H H H 29-85 Ph Me Ph H Ph H H H H H 29-86 Ph Me Ph H H Ph H H H H 29-87 Ph Me Ph H H H Ph H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 29- 88 Ph Me Ph H H H H Ph H H 29- 89 Ph Me Ph H H H H H Ph H 29- 90 Ph Me Ph H H H H H H Ph
29- 91 Me Ph Ph H H H H H H H 29- 92 Me Ph Ph Me H H H H H H 29- 93 Me Ph Ph H Me H H H H H 29- 94 Me Ph Ph H H Me H H H H 29- 95 Me Ph Ph H H H Me H H H 29- 96 Me Ph Ph H H H H Me H H 29- 97 Me Ph Ph H H H H H Me H 29- 98 Me Ph Ph H H H H H H Me 29- 99 Me Ph Ph Ph H H H H H H 29- 100 Me Ph Ph H Ph H H H H H 29- 101 Me Ph Ph H H Ph H H H H 29- 102 Me Ph Ph H H H Ph H H H 29- 103 Me Ph Ph H H H H Ph H H 29- 104 Me Ph Ph H H H H H Ph H 29- 105 Ph Ph Ph H H H H H H Ph 29- 106 Ph Ph Ph H H H H H H H 29- 107 Ph Ph Ph Me H H H H H H 29- 108 Ph Ph Ph H Me H H H H H 29- 109 Ph Ph Ph H H Me H H H H 29- 110 Ph Ph Ph H H H Me H H H 29- 111 Ph Ph Ph H H H H Me H H 29- 112 Ph Ph Ph H H H H H Me H 29- 113 Ph Ph Ph H H H H H H Me 29- 114 Ph Ph Ph Ph H H H H H H Cpd No. Rai Ra2 Ra3 ] Rbl Rb2 \ Rb3 Rb4 Rb5 Rb6 Rb7 29- 115 Ph Ph Ph H Ph H H H H H 29-116 Ph Ph Ph H H Ph H H H H 29- 117 Ph Ph Ph H H H Ph H H H 29-118 Ph Ph Ph H H H H Ph H H 29- 119 Ph Ph Ph H H H H H Ph H 29- 120 Ph Ph Ph H H H H H H Ph
Table 30
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 RbS 30- 1 Me Me Me H H H H H H H H 30-2 Me Me Me Me H H H H H H H 30-3 Me Me Me H Me H H H H H H 30-4 Me Me Me H H Me H H H H H 30-5 Me Me Me H H H Me H H H H 30-6 Me Me Me H H H H Me H H H 30-7 Me Me Me H H H H H Me H H 30-8 Me Me Me H H H H H H Me H 30-9 Me Me Me H H H H H H H Me 30-10 Me Me Me Ph H H H H H H H 30- 11 Me Me Me H Ph H H H H H H 30- 12 Me Me Me H H Ph H H H H H 30- 13 Me Me Me H H H Ph H H H H 30- 14 Me Me Me H H H H Ph H H H 30-15 Me Me Me H H H H H Ph H H 30-16 Me Me Me H H H H H H Ph H 30- 17 Me Me Me H H H H H H H Ph 30-18 Ph Me Me H H H H H H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 30- 19 Ph Me Me Me H H H H H H H 30-20 Ph Me Me H Me H H H H H H 30-21 Ph Me Me H H Me H H H H H 30-22 Ph Me Me H H H Me H H H H 30-23 Ph Me Me H H H H Me H H H 30-24 Ph Me Me H H H H H Me H H 30-25 Ph Me Me H H H H H H Me H 30-26 Ph Me Me H H H H H H H Me 30-27 Ph Me Me Ph H H H H H H H 30-28 Ph Me Me H Ph H H H H H H 30-29 Ph Me Me H H Ph H H H H H 30-30 Ph Me Me H H H Ph H H H H 30-31 Ph Me Me H H H H Ph H H H 30-32 Ph Me Me H H H H H Ph H H 30-33 Ph Me Me H H H H H H Ph H 30-34 Ph Me Me H H H H H H H Ph
30-35 Me Ph Me H H H H H H H H 30-36 Me Ph Me Me H H H H H H H 30-37 Me Ph Me H Me H H H H H H 30-38 Me Ph Me H H Me H H H H H 30-39 Me Ph Me H H H Me H H H H 30-40 Me Ph Me H H H H Me H H H 30-41 Me Ph Me H H H H H Me H H 30-42 Me Ph Me H H H H H H Me H 30-43 Me Ph Me H H H H H H H Me 30-44 Me Ph Me Ph H H H H H H H 30-45 Me Ph Me H Ph H H H H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 30-46 Me Ph Me H H Ph H H H H H 30-47 Me Ph Me H H H Ph H H H H 30-48 Me Ph Me H H H H Ph H H H 30-49 Me Ph Me H H H H H Ph H H 30-50 Me Ph Me H H H H H H Ph H 30-51 Me Ph Me H H H H H H H Ph 30-52 Ph Ph Me H H H H H H H H 30-53 Ph Ph Me Me H H H H H H H 30-54 Ph Ph Me H Me H H H H H H 30-55 Ph Ph Me H H Me H H H H H 30-56 Ph Ph Me H H H Me H H H H 30-57 Ph Ph Me H H H H Me H H H 30-58 Ph Ph Me H H H H H Me H H 30-59 Ph Ph Me H H H H H H Me H 30-60 Ph Ph Me H H H H H H H Me 30-61 Ph Ph Me Ph H H H H H H H 30-62 Ph Ph Me H Ph H H H H H H 30-63 Ph Ph Me H H Ph H H H H H 30-64 Ph Ph Me H H H Ph H H H H 30-65 Ph Ph Me H H H H Ph H H H 30-66 Ph Ph Me H H H H H Ph H H 30-67 Ph Ph Me H H H H H H Ph H 30-68 Ph Ph Me H H H H H H H Ph
30-69 Me Me Ph H H H H H H H H 30-70 Me Me Ph Me H H H H H H H 30-71 Me Me Ph H Me H H H H H H 30-72 Me Me Ph H H Me H H H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 30-73 Me Me Ph H H H Me H H H H 30-74 Me Me Ph H H H H Me H H H 30-75 Me Me Ph H H H H H Me H H 30-76 Me Me Ph H H H H H H Me H 30-77 Me Me Ph H H H H H H H Me 30-78 Me Me Ph Ph H H H H H H H 30-79 Me Me Ph H Ph H H H H H H 30-80 Me Me Ph H H Ph H H H H H 30-81 Me Me Ph H H H Ph H H H H 30-82 Me Me Ph H H H H Ph H H H 30-83 Me Me Ph H H H H H Ph H H 30-84 Me Me Ph H H H H H H Ph H 30-85 Me Me Ph H H H H H H H Ph 30-86 Ph Me Ph H H H H H H H H 30-87 Ph Me Ph Me H H H H H H H 30-88 Ph Me Ph H Me H H H H H H 30-89 Ph Me Ph H H Me H H H H H 30-90 Ph Me Ph H H H Me H H H H 30-91 Ph Me Ph H H H H Me H H H 30-92 Ph Me Ph H H H H H Me H H 30-93 Ph Me Ph H H H H H H Me H 30-94 Ph Me Ph H H H H H H H Me 30-95 Ph Me Ph Ph H H H H H H H 30-96 Ph Me Ph H Ph H H H H H H 30-97 Ph Me Ph H H Ph H H H H H 30-98 Ph Me Ph H H H Ph H H H H 30-99 Ph Me Ph H H H H Ph H H H 30- 100 Ph Me Ph H H H H H Ph H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 30- 101 Ph Me Ph H H H H H H Ph H 30- 102 Ph Me Ph H H H H H H H Ph
30- 103 Me Ph Ph H H H H H H H H 30- 104 Me Ph Ph Me H H H H H H H 30- 105 Me Ph Ph H Me H H H H H H 30- 106 Me Ph Ph H H Me H H H H H 30- 107 Me Ph Ph H H H Me H H H H 30- 108 Me Ph Ph H H H H Me H H H 30- 109 Me Ph Ph H H H H H Me H H 30- 110 Me Ph Ph H H H H H H Me H 30- 111 Me Ph Ph H H H H H H H Me 30- 112 Me Ph Ph Ph H H H H H H H 30- 113 Me Ph Ph H Ph H H H H H H 30- 114 Me Ph Ph H H Ph H H H H H 30- 115 Me Ph Ph H H H Ph H H H H 30- 116 Me Ph Ph H H H H Ph H H H 30- 117 Me Ph Ph H H H H H Ph H H 30- 118 Me Ph Ph H H H H H H Ph H 30- 119 Me Ph Ph H H H H H H H Ph 30- 120 Ph Ph Ph H H H H H H H H 30- 121 Ph Ph Ph Me H H H H H H H 30- 122 Ph Ph Ph H Me H H H H H H 30- 123 Ph Ph Ph H H Me H H H H H 30- 124 Ph Ph Ph H H H Me H H H H 30- 125 Ph Ph Ph H H H H Me H H H 30- 126 Ph Ph Ph H H H H H Me H H 30- 127 Ph Ph Ph H H H H H H Me H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 30- 128 Ph Ph Ph H H H H H H H Me 30- 129 Ph Ph Ph Ph H H H H H H H 30- 130 Ph Ph Ph H Ph H H H H H H 30- 131 Ph Ph Ph H H Ph H H H H H 30- 132 Ph Ph Ph H H H Ph H H H H 30- 133 Ph Ph Ph H H H H Ph H H H 30- 134 Ph Ph Ph H H H H H Ph H H 30- 135 Ph Ph Ph H H H H H H Ph H 30- 136 Ph Ph Ph H H H H H H H Ph
Table 31
Cpd No. Rai Ra2 Rbl Rb2 Rb3 Rb4 Rb5 31-1 Me H H H H H H 31-2 Me H Me H H H H 31-3 Me H H Me H H H 31-4 Me H H H Me H H 31-5 Me H H H H Me H 31-6 Me H H H H H Me 31-7 Me H Ph H H H H 31-8 Me H H Ph H H H 31-9 Me H H H Ph H H 31-10 Me H H H H Ph H 31-11 Me H H H H H Ph 31-12 Ph H H H H H H 31-13 Ph H Me H H H H 31-14 Ph H H Me H H H 31-15 Ph H H H Me H H Cpd No. Rai Ra2 Rbl Rb2 Rb3 Rb4 Rb5 31-16 Ph H H H H Me H 31- 17 Ph H H H H H Me 31-18 Ph H Ph H H H H 31-19 Ph H H Ph H H H 31-20 Ph H . H H Ph H H 31-21 Ph H H H H Ph H 31-22 Ph H H H H H Ph
31-23 Me Me H H H H H 31-24 Me Me Me H H H H 31-25 Me Me H Me H H H 31-26 Me Me H H Me H H 31-27 Me Me H H H Me H 31-28 Me Me H H H H Me 31-29 Me Me Ph H H H H 31-30 Me Me H Ph H H H 31-31 Me Me H H Ph H H 31-32 Me Me H H H Ph H 31-33 Me Me H H H H Ph 31-34 Ph Me H H H H H 31-35 Ph Me Me H H H H 31-36 Ph Me H Me H H H 31-37 Ph Me H H Me H H 31-38 Ph Me H H H Me H 31-39 Ph Me H H H H Me 31-40 Ph Me Ph H H H H 31-41 Ph Me H Ph H H H 31-42 Ph Me H H Ph H H Cpd No. Rai Ra2 Rbl Rb2 Rb3 Rb4 Rb5 31-43 Ph Me H H H Ph H 31-44 Ph Me H H H H Ph
31-45 Me Ph H H H H H 31-46 Me Ph Me H H H H 31-47 Me Ph H Me H H H 31-48 Me Ph H H Me H H 31-49 Me Ph H H H Me H 31-50 Me Ph H H H H Me 31-51 Me Ph Ph H H H H 31-52 Me Ph H Ph H H H 31-53 Me Ph H H Ph H H 31-54 Me Ph H H H Ph H 31-55 Me Ph H H H H Ph 31-56 Ph Ph H H H H H 31-57 Ph Ph Me H H H H 31-58 Ph Ph H Me H H H 31-59 Ph Ph H H Me H H 31-60 Ph Ph H H H Me H 31-61 Ph Ph H H H H Me 31-62 Ph Ph Ph H H H H 31-63 Ph Ph H Ph H H H 31-64 Ph Ph H H Ph H H 31-65 Ph Ph H H H Ph H 31-66 Ph Ph H H H H Ph
Table 32
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 32- 1 H H H H H H H H 32-2 H H H Me H H H H 32-3 H H H H Me H H H 32-4 H H H H H Me H H 32-5 H H H H H H Me H 32-6 H H H H H H H Me 32-7 H H H Ph H H H H 32-8 H H H H Ph H H H 32-9 H H H H H Ph H H 32- 10 H H H H H H Ph H 32- 11 H H H H H H H Ph
32- 12 Me H H H H H H H 32- 13 Me H H Me H H H H 32-14 Me H H H Me H H H 32- 15 Me H H H H Me H H 32-16 Me H H H H H Me H 32- 17 Me H H H H H H Me 32- 18 Me H H Ph H H H H 32- 19 Me H H H Ph H H H 32-20 Me H H H H Ph H H 32-21 Me H H H H H Ph H 32-22 Me H H H H H H Ph
32-23 H Me H H H H H H 32-24 H Me H Me H H H H 32-25 H Me H H Me H H H 32-26 H Me H H H Me H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 32-27 H Me H H H H Me H 32-28 H Me H H H H H Me 32-29 H Me H Ph H H H H 32-30 H Me H H Ph H H H 32-31 H Me H H H Ph H H 32-32 H Me H H H H Ph H 32-33 H Me H H H H H Ph
32-34 H H Me H H H H H 32-35 H H Me Me H H H H 32-36 H H Me H Me H H H 32-37 H H Me H H Me H H 32-38 H H Me H H H Me H 32-39 H H Me H H H H Me 32-40 H H Me Ph H H H H 32-41 H H Me H Ph H H H 32-42 H H Me H H Ph H H 32-43 H H Me H H H Ph H 32-44 H H Me H H H H Ph
32-45 Ph H H H H H H H 32-46 Ph H H Me H H H H 32-47 Ph H H H Me H H H 32-48 Ph H H H H Me H H 32-49 Ph H H H H H Me H 32-50 Ph H H H H H H Me 32-51 Ph H H Ph H H H H 32-52 Ph H H H Ph H H H Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 32-53 Ph H H H H Ph H H 32-54 Ph H H H H H Ph H 32-55 Ph H H H H H H Ph
32-56 H Ph H H H H H H 32-57 H Ph H Me H H H H 32-58 H Ph H H Me H H H 32-59 H Ph H H H Me H H 32-60 H Ph H H H H Me H 32-61 H Ph H H H H H Me 32-62 H Ph H Ph H H H H 32-63 H Ph H H Ph H H H 32-64 H Ph H H H Ph H H 32-65 H Ph H H H H Ph H 32-66 H Ph H H H H H Ph
32-67 H H Ph H H H H H 32-68 H H Ph Me H H H H 32-69 H H Ph H Me H H H 32-70 H H Ph H H Me H H 32-71 H H Ph H H H Me H 32-72 H H Ph H H H H Me 32-73 H H Ph Ph H H H H 32-74 H H Ph H Ph H H H 32-75 H H Ph H H Ph H H 32-76 H H Ph H H H Ph H 32-77 H H Ph H H H H Ph Table 33
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 33-1 Me H H H H H H H H Me Me 33-2 Me H H Me H H H H H Me Me 33-3 Me H H H Me H H H H Me Me 33-4 Me H H H H Me H H H Me Me 33-5 Me H H H H H Me H H Me Me 33-6 Me H H H H H H Me H Me Me 33-7 Me H H H H H H H Me Me Me 33-8 Me H H Ph H H H H H Me Me 33-9 Me H H H Ph H H H H Me Me 33- 10 Me H H H H Ph H H H Me Me 33-11 Me H H H H H Ph H H Me Me 33-12 Me H H H H H H Ph H Me Me 33-13 Me H H H H H H H Ph Me Me 33-14 Ph H H H H H H H H Me Me 33-15 Ph H H Me H H H H H Me Me 33-16 Ph H H H Me H H H H Me Me 33-17 Ph H H H H Me H H H Me Me 33- 18 Ph H H H H H Me H H Me Me 33- 19 Ph H H H H H H Me H Me Me 33-20 Ph H H H H H H H Me Me Me 33-21 Ph H H Ph H H H H H Me Me 33-22 Ph H H H Ph H H H H Me Me 33-23 Ph H H H H Ph H H H Me Me 33-24 Ph H H H H H Ph H H Me Me 33-25 Ph H H H H H H Ph H Me Me 33-26 Ph H H H H H H H Ph Me Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 33-27 Me Me H H H H H H H Me Me 33-28 Me Me H Me H H H H H Me Me 33-29 Me Me H H Me H H H H Me Me 33-30 Me Me H H H Me H H H Me Me 33-31 Me Me H H H H Me H H Me Me 33-32 Me Me H H H H H Me H Me Me 33-33 Me Me H H H H H H Me Me Me 33-34 Me Me H Ph H H H H H Me Me 33-35 Me Me H H Ph H H H H Me Me 33-36 Me Me H H H Ph H H H Me Me 33-37 Me Me H H H H Ph H H Me Me 33-38 Me Me H H H H H Ph H Me Me 33-39 Me Me H H H H H H Ph Me Me 33-40 Ph Me H H H H H H H Me Me 33-41 Ph Me H Me H H H H H Me Me 33-42 Ph Me H H Me H H H H Me Me 33-43 Ph Me H H H Me H H H Me Me 33-44 Ph Me H H H H Me H H Me Me 33-45 Ph Me H H H H H Me H Me Me 33-46 Ph Me H H H H H H Me Me Me 33-47 Ph Me H Ph H H H H H Me Me 33-48 Ph Me H H Ph H H H H Me Me 33-49 Ph Me H H H Ph H H H Me Me 33-50 Ph Me H H H H Ph H H Me Me 33-51 Ph Me H H H H H Ph H Me Me 33-52 Ph Me H H H H H H Ph Me Me
33-53 Me H Me H H H H H H Me Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 33-54 Me H Me Me H H H H H Me Me 33-55 Me H Me H Me H H H H Me Me 33-56 Me H Me H H Me H H H Me Me 33-57 Me H Me H H H Me H H Me Me 33-58 Me H Me H H H H Me H Me Me 33-59 Me H Me H H H H H Me Me Me 33-60 Me H Me Ph H H H H H Me Me 33-61 Me H Me H Ph H H H H Me Me 33-62 Me H Me H H Ph H H H Me Me 33-63 Me H Me H H H Ph H H Me Me 33-64 Me H Me H H H H Ph H Me Me 33-65 Me H Me H H H H H Ph Me Me 33-66 Ph H Me H H H H H H Me Me 33-67 Ph H Me Me H H H H H Me Me 33-68 Ph H Me H Me H H H H Me Me 33-69 Ph H Me H H Me H H H Me Me 33-70 Ph H Me H H H Me H H Me Me 33-71 Ph H Me H H H H Me H Me Me 33-72 Ph H Me H H H H H Me Me Me 33-73 Ph H Me Ph H H H H H Me Me 33-74 Ph H Me H Ph H H H H Me Me 33-75 Ph H Me H H Ph H H H Me Me 33-76 Ph H Me H H H Ph H H Me Me 33-77 Ph H Me H H H H Ph H Me Me 33-78 Ph H Me H H H H H Ph Me Me
33-79 Me Ph H H H H H H H Me Me 33-80 Me Ph H Me H H H H H Me Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 33-81 Me Ph H H Me H H H H Me Me 33-82 Me Ph H H H Me H H H Me Me 33-83 Me Ph H H H H Me H H Me Me 33-84 Me Ph H H H H H Me H Me Me 33-85 Me Ph H H H H H H Me Me Me 33-86 Me Ph H Ph H H H H H Me Me 33-87 Me Ph H H Ph H H H H Me Me 33-88 Me Ph H H H Ph H H H Me Me 33-89 Me Ph H H H H Ph H H Me Me 33-90 Me Ph H H H H H Ph H Me Me 33-91 Me Ph H H H H H H Ph Me Me 33-92 Ph Ph H H H H H H H Me Me 33-93 Ph Ph H Me H H H H H Me Me 33-94 Ph Ph H H Me H H H H Me Me 33-95 Ph Ph H H H Me H H H Me Me 33-96 Ph Ph H H H H Me H H Me Me 33-97 Ph Ph H H H H H Me H Me Me 33-98 Ph Ph H H H H H H Me Me Me 33-99 Ph Ph H Ph H H H H H Me Me 33- 100 Ph Ph H H Ph H H H H Me Me 33- 101 Ph Ph H H H Ph H H H • Me Me 33- 102 Ph Ph H H H H Ph H H Me Me 33- 103 Ph Ph H H H H H Ph H Me Me 33- 104 Ph Ph H H H H H H Ph Me Me
33- 105 Me H Ph H H H H H H Me Me 33- 106 Me H Ph Me H H H H H Me Me 33- 107 Me H Ph H Me H H H H Me Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 33- 108 Me H Ph H H Me H H H Me Me 33- 109 Me H Ph H H H Me H H Me Me 33- 110 Me H Ph H H H H Me H Me Me 33- 111 Me H Ph H H H H H Me Me Me 33- 112 Me H Ph Ph H H H H H Me Me 33- 113 Me H Ph H Ph H H H H Me Me 33- 114 Me H Ph H H Ph H H H Me Me 33- 115 Me H Ph H H H Ph H H Me Me 33- 116 Me H Ph H H H H Ph H Me Me 33- 117 Me H Ph H H H H H Ph Me Me 33- 118 Ph H Ph H H H H H H Me Me 33- 119 Ph H Ph Me H H H H H Me Me 33- 120 Ph H Ph H Me H H H H Me Me 33- 121 Ph H Ph H H Me H H H Me Me 33- 122 Ph H Ph H H H Me H H Me Me 33- 123 Ph H Ph H H H H Me H Me Me 33- 124 Ph H Ph H H H H H Me Me Me 33- 125 Ph H Ph Ph H H H H H Me Me 33- 126 Ph H Ph H Ph H H H H Me Me 33- 127 Ph H Ph H H Ph H H H Me Me 33- 128 Ph H Ph H H H Ph H H Me Me 33- 129 Ph H Ph H H H H Ph H Me Me 33- 130 Ph H Ph H H H H H Ph Me Me
Table 34
Cpd No . Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 34- 1 Me H H H H H H H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 34-2 Me H H H Me H H H H H Me Me 34-3 Me H H H H Me H H H H Me Me 34-4 Me H H H H H Me H H H Me Me 34-5 Me H H H H H H Me H H Me Me 34-6 Me H H H H H H H Me H Me Me 34-7 Me H H H H H H H H Me Me Me 34-8 Me H H H Ph H H H H H Me Me 34-9 Me H H H H Ph H H H H Me Me 34-10 Me H H H H H Ph H H H Me Me 34-11 Me H H H H H H Ph H H Me Me 34-12 Me H H H H H H H Ph H Me Me 34-13 Me H H H H H H H H Ph Me Me 34-14 Ph H H H H H H H H H Me Me 34- 15 Ph H H H Me H H H H H Me Me 34-16 Ph H H H H Me H H H H Me Me 34-17 Ph H H H H H Me H H H Me Me 34-18 Ph H H H H H H Me H H Me Me 34-19 Ph H H H H H H H Me H Me Me 34-20 Ph H H H H H H H H Me Me Me 34-21 Ph H H H Ph H H H H H Me Me 34-22 Ph H H H H Ph H H H H Me Me 34-23 Ph H H H H H Ph H H H Me Me 34-24 Ph H H H H H H Ph H H Me Me 34-25 Ph H H H H H H H Ph H Me Me 34-26 Ph H H H H H H H H Ph Me Me
34-27 Me Me H H H H H H H H Me Me 34-28 Me Me H H Me H H H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 34-29 Me Me H H H Me H H H H Me Me 34-30 Me Me H H H H Me H H H Me Me 34-31 Me Me H H H H H Me H H Me Me 34-32 Me Me H H H H H H Me H Me Me 34-33 Me Me H H H H H H H Me Me Me 34-34 Me Me H H Ph H H H H H Me Me 34-35 Me Me H H H Ph H H H H Me Me 34-36 Me Me H H H H Ph H H H Me Me 34-37 Me Me H H H H H Ph H H Me Me 34-38 Me Me H H H H H H Ph H Me Me 34-39 Me Me H H H H H H H Ph Me Me 34-40 Ph Me H H H H H H H H Me Me 34-41 Ph Me H H Me H H H H H Me Me 34-42 Ph Me H H H Me H H H H Me Me 34-43 Ph Me H H H H Me H H H Me Me 34-44 Ph Me H H H H H Me H H Me Me 34-45 Ph Me H H H H H H Me H Me Me 34-46 Ph Me H H H H H H H Me Me Me 34-47 Ph Me H H Ph H H H H H Me Me 34-48 Ph Me H H H Ph H H H H Me Me 34-49 Ph Me H H H H Ph H H H Me Me 34-50 Ph Me H H H H H Ph H H Me Me 34-51 Ph Me H H H H H H Ph H Me Me 34-52 Ph Me H H H H H H H Ph Me Me
34-53 Me H Me H H H H H H H Me Me 34-54 Me H Me H Me H H H H H Me Me 34-55 Me H Me H H Me H H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 RbS 34-56 Me H Me H H H Me H H H Me Me 34-57 Me H Me H H H H Me H H Me Me 34-58 Me H Me H H H H H Me H Me Me 34-59 Me H Me H H H H H H Me Me Me 34-60 Me H Me H Ph H H H H H Me Me 34-61 Me H Me H H Ph H H H H Me Me 34-62 Me H Me H H H Ph H H H Me Me 34-63 Me H Me H H H H Ph H H Me Me 34-64 Me H Me H H H H H Ph H Me Me 34-65 Me H Me H H H H H H Ph Me Me 34-66 Ph H Me H H H H H H H Me Me 34-67 Ph H Me H Me H H H H H Me Me 34-68 Ph H Me H H Me H H H H Me Me 34-69 Ph H Me H H H Me H H H Me Me 34-70 Ph H Me H H H H Me H H Me Me 34-71 Ph H Me H H H H H Me H Me Me 34-72 Ph H Me H H H H H H Me Me Me 34-73 Ph H Me H Ph H H H H H Me Me 34-74 Ph H Me H H Ph H H H H Me Me 34-75 Ph H Me H H H Ph H H H Me Me 34-76 Ph H Me H H H H Ph H H Me Me 34-77 Ph H Me H H H H H Ph H Me Me 34-78 Ph H Me H H H H H H Ph Me Me
34-79 Me H H Me H H H H H H Me Me 34-80 Me H H Me Me H H H H H Me Me 34-81 Me H H Me H Me H H H H Me Me 34-82 Me H H Me H H Me H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 34-83 Me H H Me H H H Me H H Me Me 34-84 Me H H Me H H H H Me H Me Me 34-85 Me H H Me H H H H H Me Me Me 34-86 Me H H Me Ph H H H H H Me Me 34-87 Me H H Me H Ph H H H H Me Me 34-88 Me H H Me H H Ph H H H Me Me 34-89 Me H H Me H H H Ph H H Me Me 34-90 Me H H Me H H H H Ph H Me Me 34-91 Me H H Me H H H H H Ph Me Me 34-92 Ph H H Me H H H H H H Me Me 34-93 Ph H H Me Me H H H H H Me Me 34-94 Ph H H Me H Me H H H H Me Me 34-95 Ph H H Me H H Me H H H Me Me 34-96 Ph H H Me H H H Me H H Me Me 34-97 Ph H H Me H H H H Me H Me Me 34-98 Ph H H Me H H H H H Me Me Me 34-99 Ph H H Me Ph H H H H H Me Me 34- 100 Ph H H Me H Ph H H H H Me Me 34- 101 Ph H H Me H H Ph H H H Me Me 34- 102 Ph H H Me H H H Ph H H Me Me 34- 103 Ph H H Me H H H H Ph H Me Me 34- 104 Ph H H Me H H H H H Ph Me Me
34- 105 Me Ph H H H H H H H H Me Me 34- 106 Me Ph H H Me H H H H H Me Me 34- 107 Me Ph H H H Me H H H H Me Me 34- 108 Me Ph H H H H Me H H H Me Me 34- 109 Me Ph H H H H H Me H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 RbS 34- 110 Me Ph H H H H H H Me H Me Me 34- 111 Me Ph H H H H H H H Me Me Me 34- 112 Me Ph H H Ph H H H H H Me Me 34- 113 Me Ph H H H Ph H H H H Me Me 34- 114 Me Ph H H H H Ph H H H Me Me 34- 115 Me Ph H H H H H Ph H H Me Me 34- 116 Me Ph H H H H H H Ph H Me Me 34- 117 Me Ph H H H H H H H Ph Me Me 34- 118 Ph Ph H H H H H H H H Me Me 34- 119 Ph Ph H H Me H H H H H Me Me 34- 120 Ph Ph H H H Me H H H H Me Me 34- 121 Ph Ph H H H H Me H H H Me Me 34- 122 Ph Ph H H H H H Me H H Me Me 34- 123 Ph Ph H H H H H H Me H Me Me 34- 124 Ph Ph H H H H H H H Me Me Me 34- 125 Ph Ph H H Ph H H H H H Me Me 34- 126 Ph Ph H H H Ph H H H H Me Me 34- 127 Ph Ph H H H H Ph H H H Me Me 34- 128 Ph Ph H H H H H Ph H H Me Me 34- 129 Ph Ph H H H H H H Ph H Me Me 34- 130 Ph Ph H H H H H H H Ph Me Me
34- 131 Me H Ph H H H H H H H Me Me 34- 132 Me H Ph H Me H H H H H Me Me 34- 133 Me H Ph H H Me H H H H Me Me 34- 134 Me H Ph H H H Me H H H Me Me 34- 135 Me H Ph H H H H Me H H Me Me 34- 136 Me H Ph H H H H H Me H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 RbS 34- 137 Me H Ph H H H H H H Me Me Me 34- 138 Me H Ph H Ph H H H H H Me Me 34- 139 Me H Ph H H Ph H H H H Me Me 34- 140 Me H Ph H H H Ph H H H Me Me 34- 141 Me H Ph H H H H Ph H H Me Me 34- 142 Me H Ph H H H H H Ph H Me Me 34- 143 Me H Ph H H H H H H Ph Me Me 34- 144 Ph H Ph H H H H H H H Me Me 34- 145 Ph H Ph H Me H H H H H Me Me 34- 146 Ph H Ph H H Me H H H H Me Me 34- 147 Ph H Ph H H H Me H H H Me Me 34- 148 Ph H Ph H H H H Me H H Me Me 34- 149 Ph H Ph H H H H H Me H Me Me 34- 150 Ph H Ph H H H H H H Me Me Me 34- 151 Ph H Ph H Ph H H H H H Me Me 34- 152 Ph H Ph H H Ph H H H H Me Me 34- 153 Ph H Ph H H H Ph H H H Me Me 34- 154 Ph H Ph H H H H Ph H H Me Me 34- 155 Ph H Ph H H H H H Ph H Me Me 34- 156 Ph H Ph H H H H H H Ph Me Me
34- 157 Me H H Ph H H H H H H Me Me 34- 158 Me H H Ph Me H H H H H Me Me 34- 159 Me H H Ph H Me H H H H Me Me 34- 160 Me H H Ph H H Me H H H Me Me 34- 161 Me H H Ph H H H Me H H Me Me 34- 162 Me H H Ph H H H H Me H Me Me 34- 163 Me H H Ph H H H H H Me Me Me Cpd No. Rai Ra2 Ra3 Ra4 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 34- 164 Me H H Ph Ph H H H H H Me Me 34- 165 Me H H Ph H Ph H H H H Me Me 34- 166 Me H H Ph H H Ph H H H Me Me 34- 167 Me H H Ph H H H Ph H H Me Me 34- 168 Me H H Ph H H H H Ph H Me Me 34- 169 Me H H Ph H H H H H Ph Me Me 34- 170 Ph H H Ph H H H H H H Me Me 34- 171 Ph H H Ph Me H H H H H Me Me 34- 172 Ph H H Ph H Me H H H H Me Me 34- 173 Ph H H Ph H H Me H H H Me Me 34- 174 Ph H H Ph H H H Me H H Me Me 34- 175 Ph H H Ph H H H H Me H Me Me 34- 176 Ph H H Ph H H H H H Me Me Me 34- 177 Ph H H Ph Ph H H H H H Me Me 34- 178 Ph H H Ph H Ph H H H H Me Me 34- 179 Ph H H Ph H H Ph H H H Me Me 34- 180 Ph H H Ph H H H Ph H H Me Me 34- 181 Ph H H Ph H H H H Ph H Me Me 34- 182 Ph H H Ph H H H H H Ph Me Me
Table 35
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Rbl Rb2 Rb3 Rb4 RbS Rb6 Rb7 Rb8 35- 1 Me : H H H H H H H H H H Me Me 35- 2 Me ! H H H H Me H H H H H Me Me 35- 3 Me ! H H H H H Me H H H H Me Me 35- 4 Me ! H H H H H H ] Me H H H Me Me 35- 5 Me s H H H H H H H Me H H Me Me -6 Me H H H H H H H H Me H Me Me-7 Me H H H H H H H H H Me Me Me-8 Me H H H H Ph H H H H H Me Me-9 Me H H H H H Ph H H H H Me Me-10 Me H H H H H H Ph H H H Me Me-11 Me H H H H H H H Ph H H Me Me-12 Me H H H H H H H H Ph H Me Me-13 Me H H H H H H H H H Ph Me Me-14 Ph H H H H H H H H H H Me Me- 15 Ph H H H H Me H H H H H Me Me- 16 Ph H H H H H Me H H H H Me Me- 17 Ph H H H H H H Me H H H Me Me- 18 Ph H H H H H H H Me H H Me Me- 19 Ph H H H H H H H H Me H Me Me-20 Ph H H H H H H H H H Me Me Me-21 Ph H H H H Ph H H H H H Me Me-22 Ph H H H H H Ph H H H H Me Me-23 Ph H H H H H H Ph H H H Me Me-24 Ph H H H H H H H Ph H H Me Me-25 Ph H H H H H H H H Ph H Me Me-26 Ph H H H H H H H H H Ph Me Me -27 Me Me H H H H H H H H H Me Me-28 Me Me H HH H Me H H H H H Me Me-29 Me Me H H H H Me H H H H Me Me-30 Me Me H H H H H Me H H H Me Me-31 Me Me H HH H H H H Me H H Me Me-32 Me Me H H H H H H H Me H Me Me-33 Me Me H H H H H H H H Me Me Me -34 Me Me H H H Ph H H H H H Me Me-35 Me Me H H H H Ph H H H H Me Me-36 Me Me H H H H H Ph H H H Me Me-37 Me Me H H H H H H Ph H H Me Me-38 Me Me H H H H H H H Ph H Me Me-39 Me Me H H H H H H H H Ph Me Me-40 Ph Me H H H H H H H H H Me Me-41 Ph Me H H H Me H H H H H Me Me-42 Ph Me H H H H Me H H H H Me Me-43 Ph Me H H H H H Me H H H Me Me-44 Ph Me H H H H H H Me H H Me Me-45 Ph Me H H H H H H H Me H Me Me-46 Ph Me H H H H H H H H Me Me Me-47 Ph Me H H H Ph H H H H H Me Me-48 Ph Me H H H H Ph H H H H Me Me-49 Ph Me H H H H H Ph H H H Me Me-50 Ph Me H H H H H H Ph H H Me Me-51 Ph Me H H H H H H H Ph H Me Me-52 Ph Me H H H H H H H H Ph Me Me -53 Me H Me H H H H H H H H Me Me-54 Me H Me H H Me H H H H H Me Me-55 Me H Me H H H Me H H H H Me Me-56 Me H Me H H H H Me H H H Me Me-57 Me H Me H H H H H Me H H Me Me-58 Me H Me HH H H H H H Me H Me Me-59 Me H Me HH H H H H H H Me Me Me-60 Me H Me HH H Ph H H H H H Me Me-61 Me H Me HH H H Ph H H H H Me Me -62 Me H Me H H H H Ph H H H Me Me-63 Me H Me H H H H H Ph H H Me Me-64 Me H Me H H H H H H Ph H Me Me-65 Me H Me H H H H H H H Ph Me Me-66 Ph H Me H H H H H H H H Me Me-67 Ph H Me H H Me H H H H H Me Me-68 Ph H Me H H H Me H H H H Me Me-69 Ph H Me H H H H Me H H H Me Me-70 Ph H Me H H H H H Me H H Me Me-71 Ph H Me H H H H H H Me H Me Me-72 Ph H Me H H H H H H H Me Me Me-73 Ph H Me H H Ph H H H H H Me Me-74 Ph H Me H H H Ph H H H H Me Me-75 Ph H Me H H H H Ph H H H Me Me-76 Ph H Me H H H H H Ph H H Me Me-77 Ph H Me H H H H H H Ph H Me Me-78 Ph H Me H H H H H H H Ph Me Me - 79 Me H H Me H H H H H H H Me Me- 80 Me H H Me H Me H H H H H Me Me-81 Me H H Me H H Me H H H H Me Me- 82 Me H H Me H H H Me H H H Me Me- 83 Me H H Me H H H H Me H H Me Me- 84 Me H H Me H H H H H Me H Me Me- 85 Me H H Me H H H H H H Me Me Me- 86 Me H H Me H Ph H H H H H Me Me- 87 Me H H Me H H Ph H H H H Me Me- Me H H Me H H H Ph H H H Me Me-89 Me H H Me H H H H Ph H H Me Me - 90 Me H H Me H H H H H Ph H Me Me- 91 Me H H Me H H H H H H Ph Me Me- 92 Ph H H Me H H H H H H H Me Me- 93 Ph H H Me H Me H H H H H Me Me- 94 Ph H H Me H H Me H H H H Me Me- 95 Ph H H Me H H H Me H H H Me Me- 96 Ph H H Me H H H H Me H H Me Me- 97 Ph H H Me H H H H H Me H Me Me- 98 Ph H H Me H H H H H H Me Me Me- 99 Ph H H Me H Ph H H H H H Me Me- 100 Ph H H Me H H Ph H H H H Me Me- 101 Ph H H Me H H H Ph H H H Me Me- 102 Ph H H Me H H H H Ph H H Me Me- 103 Ph H H Me H H H H H Ph H Me Me- 104 Ph H H Me H H H H H H Ph Me Me - 105 Me H H H Me H H H H H H Me Me- 106 Me H H H Me Me H H H H H Me Me- 107 Me H H H Me H Me H H H H Me Me- 108 Me H H H Me H H Me H H H Me Me- 109 Me H H H Me H H H Me H H Me Me- 110 Me H H H Me H H H H Me H Me Me- 111 Me H H H Me H H H H H Me Me Me- 112 Me H H H Me Ph H H H H H Me Me- 113 Me H H H Me H Ph H H H H Me Me- 114 Me H H H Me H H Ph H H H Me Me- 115 Me H H H Me H H H Ph H H Me Me- 116 Me H H H Me H H H H Ph H Me Me- 117 Me H H H Me H H H H H Ph Me Me - 118 Ph H H H Me H H H H H H Me Me- 119 Ph H H H Me Me H H H H H Me Me- 120 Ph H H H Me H Me H H H H Me Me- 121 Ph H H H Me H H Me H H H Me Me- 122 Ph H H H Me H H H Me H H Me Me- 123 Ph H H H Me H H H H Me H Me Me- 124 Ph H H H Me H H H H H Me Me Me- 125 Ph H H H Me Ph H H H H H Me Me- 126 Ph H H H Me H Ph H H H H Me Me- 127 Ph H H H Me H H Ph H H H Me Me- 128 Ph H H H Me H H H Ph H H Me Me- 129 Ph H H H Me H H H H Ph H Me Me- 130 Ph H H H Me H H H H H Ph Me Me - 131 Me Ph H H H H H H H H H Me Me- 132 Me Ph H H H Me H H H H H Me Me- 133 Me Ph H H H H Me H H H H Me Me- 134 Me Ph H H H H H Me H H H Me Me- 135 Me Ph H H H H H H Me H H Me Me- 136 Me Ph H H H H H H H Me H Me Me- 137 Me Ph H H H H H H H H Me Me Me- 138 Me Ph H H H Ph H H H H H Me Me- 139 Me Ph H H H H Ph H H H H Me Me- 140 Me Ph H H H H H Ph H H H Me Me- 141 Me Ph H H H H H H Ph H H Me Me- 142 Me Ph H H H H H H H Ph H Me Me- 143 Me Ph H H H H H H H H Ph Me Me- 144 Ph Ph H H H H H H H H H Me Me- 145 Ph Ph H H H Me H H H H H Me Me - 146 Ph Ph H H H H Me H H H H Me Me- 147 Ph Ph H H H H H Me H H H Me Me- 148 Ph Ph H H H H H H Me H H Me Me- 149 Ph Ph H H H H H H H Me H Me Me- 150 Ph Ph H H H H H H H H Me Me Me- 151 Ph Ph H H H Ph H H H H H Me Me- 152 Ph Ph H H H H Ph H H H H Me Me- 153 Ph Ph H H H H H Ph H H H Me Me- 154 Ph Ph H H H H H H Ph H H Me Me- 155 Ph Ph H H H H H H H Ph H Me Me- 156 Ph Ph H H H H H H H H Ph Me Me - 157 Me H Ph H H H H H H H H Me Me- 158 Me H Ph H H Me H H H H H Me Me- 159 Me H Ph H H H Me H H H H Me Me- 160 Me H Ph H H H H Me H H H Me Me- 161 Me H Ph H H H H H Me H H Me Me- 162 Me H Ph H H H H H H Me H Me Me- 163 Me H Ph H H H H H H H Me Me Me- 164 Me H Ph H H Ph H H H H H Me Me- 165 Me H Ph H H H Ph H H H H Me Me- 166 Me H Ph H H H H Ph H H H Me Me- 167 Me H Ph HH H H H H Ph H H Me Me- 168 Me H Ph H H H H H H Ph H Me Me- 169 Me H Ph H H H H H H H Ph Me Me- 170 Ph H Ph H H H H H H H H Me Me- 171 Ph H Ph H H Me H H H H H Me Me- 172 Ph H Ph H H H Me H H H H Me Me- 173 Ph H Ph H H H H Me H H H Me Me - 174 Ph H Ph H H H H H Me H H Me Me- 175 Ph H Ph H H H H H H Me H Me Me- 176 Ph H Ph H H H H H H H Me Me Me- 177 Ph H Ph H H Ph H H H H H Me Me- 178 Ph H Ph H H H Ph H H H H Me Me- 179 Ph H Ph H H H H Ph H H H Me Me- 180 Ph H Ph H H H H H Ph H H Me Me- 181 Ph H Ph H H H H H H Ph H Me Me- 182 Ph H Ph H H H H H H H Ph Me Me - 183 Me H H Ph H H H H H H H Me Me- 184 Me H H Ph H Me H H H H H Me Me- 185 Me H H Ph H H Me H H H H Me Me- 186 Me H H Ph H H H Me H H H Me Me- 187 Me H H Ph H H H H Me H H Me Me- 188 Me H H Ph H H H H H Me H Me Me- 189 Me H H Ph H H H H H H Me Me Me- 190 Me H H Ph H Ph H H H H H Me Me- 191 Me H H Ph H H Ph H H H H Me Me- 192 Me H H Ph H H H Ph H H H Me Me- 193 Me H H Ph H H H H Ph H H Me Me- 194 Me H H Ph H H H H H Ph H Me Me- 195 Me H H Ph H H H H H H Ph Me Me- 196 Ph H H Ph H H H H H H H Me Me- 197 Ph H H Ph H Me H H H H H Me Me- 198 Ph H H Ph H H Me H H H H Me Me- 199 Ph H H Ph H H H Me H H H Me Me- 200 Ph H H Ph H H H H Me H H Me Me- 201 Ph H H Ph H H H H H Me H Me Me - 202 Ph H H Ph H H H H H H Me Me Me- 203 Ph H H Ph H Ph H H H H H Me Me- 204 Ph H H Ph H H Ph H H H H Me Me- 205 Ph H H Ph H H H Ph H H H Me Me- 206 Ph H H Ph H H H H Ph H H Me Me- 207 Ph H H Ph H H H H H Ph H Me Me- 208 Ph H H Ph H H H H H H Ph Me Me - 209 Me H H H Ph H H H H H H Me Me- 210 Me H H H Ph Me H H H H H Me Me- 211 Me H H H Ph H Me H H H H Me Me- 212 Me H H H Ph H H Me H H H Me Me- 213 Me H H H Ph H H H Me H H Me Me- 214 Me H H H Ph H H H H Me H Me Me- 215 Me H H H Ph H H H H H Me Me Me- 216 Me H H H Ph Ph H H H H H Me Me- 217 Me H H H Ph H Ph H H H H Me Me- 218 Me H H H Ph H H Ph H H H Me Me- 219 Me H H H Ph H H H Ph H H Me Me- 220 Me H H H Ph H H H H Ph H Me Me- 221 Me H H H Ph H H H H H Ph Me Me- 222 Ph H H H Ph H H H H H H Me Me- 223 Ph H H H Ph Me H H H H H Me Me- 224 Ph H H H Ph H Me H H H H Me Me- 225 Ph H H H Ph H H Me H H H Me Me- 226 Ph H H H Ph H H H Me H H Me Me- 227 Ph H H H Ph H H H H Me H Me Me- 228 Ph H H H Ph H H H H H Me Me Me- 229 Ph H H H Ph Ph H H H H H Me Me 35- 230 Ph H H H Ph H Ph H H H H Me Me 35-231 Ph H H H Ph H H Ph H H H Me Me 35- 232 Ph H H H Ph H H H Ph H H Me Me 35- 233 Ph H H H Ph H H H H Ph H Me Me 35- 234 Ph H H H Ph H H H H H Ph Me Me
Table 36
Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 36-1 Me H H H H H H H H H H H H Me Me 36-2 Me H H H H H H Me H H H H H Me Me 36-3 Me H H H H H H H Me H H H H Me Me 36-4 Me H H H H H H H H Me H H H Me Me 36-5 Me H H H H H H H H H Me H H Me Me 36-6 Me H H H H H H H H H H Me H Me Me 36-7 Me H H H H H H H H H H H Me Me Me 36-8 Me H H H H H H Ph H H H H H Me Me 36-9 Me H H H H H H H Ph H H H H Me Me 36-10 Me H H H H H H H H Ph H H H Me Me 36-11 Me H H H H H H H H H Ph H H Me Me 36- 12 Me H H H H H H H H H H Ph H Me Me 36-13 Me H H H H H H H H H H H Ph Me Me 36- 14 Ph H H H H H H H H H H H H Me Me 36- 15 Ph H H H H H H Me H H H H H Me Me 36- 16 Ph H H H H H H H Me H H H H Me Me 36-17 Ph H H H H H H H H Me H H H Me Me 36-18 Ph H H H H H H H H H Me H H Me Me 36-19 Ph H H H H H H H H H H Me H Me Me 36-20 Ph H H H H H H H H H H H Me Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 36-21 Ph H H H H H H Ph H H H H H Me Me 36-22 Ph H H H H H H H Ph H H H H Me Me 36-23 Ph H H H H H H H H Ph H H H Me Me 36-24 Ph H H H H H H H H H Ph H H Me Me 36-25 Ph H H H H H H H H H H Ph H Me Me 36-26 Ph H H H H H H H H H H H Ph Me Me
36-27 Me Me H H H H H H H H H H H Me Me 36-28 Me Me H H H H H Me H H H H H Me Me 36-29 Me Me H H H H H H Me H H H H Me Me 36-30 Me Me H H H H H H H Me H H H Me Me 36-31 Me Me H H H H H H H H Me H H Me Me 36-32 Me Me H H H H H H H H H Me H Me Me 36-33 Me Me H H H H H H H H H H Me Me Me 36-34 Me Me H H H H H Ph H H H H H Me Me 36-35 Me Me H H H H H H Ph H H H H Me Me 36-36 Me Me H H H H H H H Ph H H H Me Me 36-37 Me Me H H H H H H H H Ph H H Me Me 36-38 Me Me H H H H H H H H H Ph H Me Me 36-39 Me Me H H H H H H H H H H Ph Me Me 36-40 Ph Me H H H H H H H H H H H Me Me 36-41 Ph Me H H H H H Me H H H H H Me Me 36-42 Ph Me H H H H H H Me H H H H Me Me 36-43 Ph Me H H H H H H H Me H H H Me Me 36-44 Ph Me H H H H H H H H Me H H Me Me 36-45 Ph Me H H H H H H H H H Me H Me Me 36-46 Ph Me H H H H H H H H H H Me Me Me 36-47 Ph Me H H H H H Ph H H H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 36-48 Ph Me H H H H H H Ph H H H H Me Me 36-49 Ph Me H H H H H H H Ph H H H Me Me 36-50 Ph Me H H H H H H H H Ph H H Me Me 36-51 Ph Me H H H H H H H H H Ph H Me Me 36-52 Ph Me H H H H H H H H H H Ph Me Me
36-53 Me H Me H H H H H H H H H H Me Me 36-54 Me H Me H H H H Me H H H H H Me Me 36-55 Me H Me H H H H H Me H H H H Me Me 36-56 Me H Me H H H H H H Me H H H Me Me 36-57 Me H Me H H H H H H H Me H H Me Me 36-58 Me H Me H H H H H H H H Me H Me Me 36-59 Me H Me H H H H H H H H H Me Me Me 36-60 Me H Me H H H H Ph H H H H H Me Me 36-61 Me H Me H H H H H Ph H H H H Me Me 36-62 Me H Me H H H H H H Ph H H H Me Me 36-63 Me H Me H H H H H H H Ph H H Me Me 36-64 Me H Me H H H H H H H H Ph H Me Me 36-65 Me H Me H H H H H H H H H Ph Me Me 36-66 Ph H Me H H H H H H H H H H Me Me 36-67 Ph H Me H H H H Me H H H H H Me Me 36-68 Ph H Me H H H H H Me H H H H Me Me 36-69 Ph H Me H H H H H H Me H H H Me Me 36-70 Ph H Me H H H H H H H Me H H Me Me 36-71 Ph H Me H H H H H H H H Me H Me Me 36-72 Ph H Me H H H H H H H H H Me Me Me 36-73 Ph H Me H H H H Ph H H H H H Me Me 36-74 Ph H Me H H H H H Ph H H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 36-75 Ph H Me H H H H H H Ph H H H Me Me 36-76 Ph H Me H H H H H H H Ph H H Me Me 36-77 Ph H Me H H H H H H H H Ph H Me Me 36-78 Ph H Me H H H H H H H H H Ph Me Me
36-79 Me H H Me H H H H H H H H H Me Me 36-80 Me H H Me H H H Me H H H H H Me Me 36-81 Me H H Me H H H H Me H H H H Me Me 36-82 Me H H Me H H H H H Me H H H Me Me 36-83 Me H H Me H H H H H H Me H H Me Me 36-84 Me H H Me H H H H H H H Me H Me Me 36-85 Me H H Me H H H H H H H H Me Me Me 36-86 Me H H Me H H H Ph H H H H H Me Me 36-87 Me H H Me H H H H Ph H H H H Me Me 36-88 'Me H H Me H H H H H Ph H H H Me Me 36-89 Me H H Me H H H H H H Ph H H Me Me 36-90 Me H H Me H H H H H H H Ph H Me Me 36-91 Me H H Me H H H H H H H H Ph Me Me 36-92 Ph H H Me H H H H H H H H H Me Me 36-93 Ph H H Me H H H Me H H H H H Me Me 36-94 Ph H H Me H H H H Me H H H H Me Me 36-95 Ph H H Me H H H H H Me H H H Me Me 36-96 Ph H H Me H H H H H H Me H H Me Me 36-97 Ph H H Me H H H H H H H Me H Me Me 36-98 Ph H H Me H H H H H H H H Me Me Me 36-99 Ph H H Me H H H Ph H H H H H Me Me 36- 100 Ph H H Me H H H H Ph H H H H Me Me 36- 101 Ph H H Me H H H H H Ph H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 36- 102 Ph H H Me H H H H H H Ph H H Me Me 36- 103 Ph H H Me H H H H H H H Ph H Me Me 36- 104 Ph H H Me H H H H H H H H Ph Me Me
36- 105 Me H H H Me H H H H H H H H Me Me 36- 106 Me H H H Me H H Me H H H H H Me Me 36- 107 Me H H H Me H H H Me H H H H Me Me 36- 108 Me H H H Me H H H H Me H H H Me Me 36- 109 Me H H H Me H H H H H Me H H Me Me 36- 110 Me H H H Me H H H H H H Me H Me Me 36- 111 Me H H H Me H H H H H H H Me Me Me 36- 112 Me H H H Me H H Ph H H H H H Me Me 36- 113 Me H H H Me H H H Ph H H H H Me Me 36- 114 Me H H H Me H H H H Ph H H H Me Me 36- 115 Me H H H Me H H H H H Ph H H Me Me 36- 116 Me H H H Me H H H H H H Ph H Me Me 36- 117 Me H H H Me H H H H H H H Ph Me Me 36- 118 Ph H H H Me H H H H H H H H Me Me 36- 119 Ph H H H Me H H Me H H H H H Me Me 36- 120 Ph H H H Me H H H Me H H H H Me Me 36- 121 Ph H H H Me H H H H Me H H H Me Me 36- 122 Ph H H H Me H H H H H Me H H Me Me 36- 123 Ph H H H Me H H H H H H Me H Me Me 36- 124 Ph H H H Me H H H H H H H Me Me Me 36- 125 Ph H H H Me H H Ph H H H H H Me Me 36- 126 Ph H H H Me H H H Ph H H H H Me Me 36- 127 Ph H H H Me H H H H Ph H H H Me Me 36- 128 Ph H H H Me H H H H H Ph H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 36- 129 Ph H H H Me H H H H H H Ph H Me Me 36- 130 Ph H H H Me H H H H H H H Ph Me Me
36- 131 Me H H H H Me H H H H H H H Me Me 36- 132 Me H H H H Me H Me H H H H H Me Me 36- 133 Me H H H H Me H H Me H H H H Me Me 36- 134 Me H H H H Me H H H Me H H H Me Me 36- 135 Me H H H H Me H H H H Me H H Me Me 36- 136 Me H H H H Me H H H H H Me H Me Me 36- 137 Me H H H H Me H H H H H H Me Me Me 36- 138 Me H H H H Me H Ph H H H H H Me Me 36- 139 Me H H H H Me H H Ph H H H H Me Me 36- 140 Me H H H H Me H H H Ph H H H Me Me 36- 141 Me H H H H Me H H H H Ph H H Me Me 36- 142 Me H H H H Me H H H H H Ph H Me Me 36- 143 Me H H H H Me H H H H H H Ph Me Me 36- 144 Ph H H H H Me H H H H H H H Me Me 36- 145 Ph H H H H Me H Me H H H H H Me Me 36- 146 Ph H H H H Me H H Me H H H H Me Me 36- 147 Ph H H H H Me H H H Me H H H Me Me 36- 148 Ph H H H H Me H H H H Me H H Me Me 36- 149 Ph H H H H Me H H H H H Me H Me Me 36- 150 Ph H H H H Me H H H H H H Me Me Me 36- 151 Ph H H H H Me H Ph H H H H H Me Me 36- 152 Ph H H H H Me H H Ph H H H H Me Me 36- 153 Ph H H H H Me H H H Ph H H H Me Me 36- 154 Ph H H H H Me H H H H Ph H H Me Me 36- 155 Ph H H H H Me H H H H H Ph H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 36- 156 Ph H H H H Me H H H H H H Ph Me Me
36- 157 Me H H H H H Me H H H H H H Me Me 36- 158 Me H H H H H Me Me H H H H H Me Me 36- 159 Me H H H H H Me H Me H H H H Me Me 36- 160 Me H H H H H Me H H Me H H H Me Me 36- 161 Me H H H H H Me H H H Me H H Me Me 36- 162 Me H H H H H Me H H H H Me H Me Me 36- 163 Me H H H H H Me H H H H H Me Me Me 36- 164 Me H H H H H Me Ph H H H H H Me Me 36- 165 Me H H H H H Me H Ph H H H H Me Me 36- 166 Me H H H H H Me H H Ph H H H Me Me 36- 167 Me H H H H H Me H H H Ph H H Me Me 36- 168 Me H H H H H Me H H H H Ph H Me Me 36- 169 Me H H H H H Me H H H H H Ph Me Me 36- 170 Ph H H H H H Me H H H H H H Me Me 36- 171 Ph H H H H H Me Me H H H H H Me Me 36- 172 Ph H H H H H Me H Me H H H H Me Me 36- 173 Ph H H H H H Me H H Me H H H Me Me 36- 174 Ph H H H H H Me H H H Me H H Me Me 36- 175 Ph H H H H H Me H H H H Me H Me Me 36- 176 Ph H H H H H Me H H H H H Me Me Me 36- 177 Ph H H H H H Me Ph H H H H H Me Me 36- 178 Ph H H H H H Me H Ph H H H H Me Me 36- 179 Ph H H H H H Me H H Ph H H H Me Me 36- 180 Ph H H H H H Me H H H Ph H H Me Me 36- 181 Ph H H H H H Me H H H H Ph H Me Me 36- 182 Ph H H H H H Me H H H H H Ph Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8
36- 183 Me Ph H H H H H H H H H H H Me Me 36- 184 Me Ph H H H H H Me H H H H H Me Me 36- 185 Me Ph H H H H H H Me H H H H Me Me 36- 186 Me Ph H H H H H H H Me H H H Me Me 36- 187 Me Ph H H H H H H H H Me H H Me Me 36- 188 Me Ph H H H H H H H H H Me H Me Me 36- 189 Me Ph H H H H H H H H H H Me Me Me 36- 190 Me Ph H H H H H Ph H H H H H Me Me 36- 191 Me Ph H H H H H H Ph H H H H Me Me 36- 192 Me Ph H H H H H H H Ph H H H Me Me 36- 193 Me Ph H H H H H H H H Ph H H Me Me 36- 194 Me Ph H H H H H H H H H Ph H Me Me 36- 195 Me Ph H H H H H H H H H H Ph Me Me 36- 196 Ph Ph H H H H H H H H H H H Me Me 36- 197 Ph Ph H H H H H Me H H H H H Me Me 36- 198 Ph Ph H H H H H H Me H H H H Me Me 36- 199 Ph Ph H H H H H H H Me H H H Me Me 36- 200 Ph Ph H H H H H H H H Me H H Me Me 36- 201 Ph Ph H H H H H H H H H Me H Me Me 36- 202 Ph Ph H H H H H H H H H H Me Me Me 36- 203 Ph Ph H H H H H Ph H H H H H Me Me 36- 204 Ph Ph H H H H H H Ph H H H H Me Me 36- 205 Ph Ph H H H H H H H Ph H H H Me Me 36- 206 Ph Ph H H H H H H H H Ph H H Me Me 36- 207 Ph Ph H H H H H H H H H Ph H Me Me 36- 208 Ph Ph H H H H H H H H H H Ph Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 36-209 Me H Ph H H H H H H H H H H Me Me 36-210 Me H Ph H H H H Me H H H H H Me Me 36-211 Me H Ph H H H H H Me H H H H Me Me 36-212 Me H Ph H H H H H H Me H H H Me Me 36-213 Me H Ph H H H H H H H Me H H Me Me 36-214 Me H Ph H H H H H H H H Me H Me Me 36-215 Me H Ph H H H H H H H H H Me Me Me 36-216 Me H Ph H H H H Ph H H H H H Me Me 36-217 Me H Ph H H H H H Ph H H H H Me Me 36-218 Me H Ph H H H H H H Ph H H H Me Me 36-219 Me H Ph H H H H H H H Ph H H Me Me 36-220 Me H Ph H H H H H H H H Ph H Me Me 36-221 Me H Ph H H H H H H H H H Ph Me Me 36-222 Ph H Ph H H H H H H H H H H Me Me 36-223 Ph H Ph H H H H Me H H H H H Me Me 36-224 Ph H Ph H H H H H Me H H H H Me Me 36-225 Ph H Ph H H H H H H Me H H H Me Me 36-226 Ph H Ph H H H H H H H Me H H Me Me 36-227 Ph H Ph H H H H H H H H Me H Me Me 36-228 Ph H Ph H H H H H H H H H Me Me Me 36-229 Ph H Ph H H H H Ph H H H H H Me Me 36-230 Ph H Ph H H H H H Ph H H H H Me Me 36-231 Ph H Ph H H H H H H Ph H H H Me Me 36-232 Ph H Ph H H H H H H H Ph H H Me Me 36-233 Ph H Ph H H H H H H H H Ph H Me Me 36-234 Ph H Ph H H H H H H H H H Ph Me Me
36-235 Me H H Ph H H H H H H H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 36- 236 Me H H Ph H H H Me H H H H H Me Me 36- 237 Me H H Ph H H H H Me H H H H Me Me 36- 238 Me H H Ph H H H H H Me H H H Me Me 36- 239 Me H H Ph H H H H H H Me H H Me Me 36- 240 Me H H Ph H H H H H H H Me H Me Me 36- 241 Me H H Ph H H H H H H H H Me Me Me 36- 242 Me H H Ph H H H Ph H H H H H Me Me 36- 243 Me H H Ph H H H H Ph H H H H Me Me 36- 244 Me H H Ph H H H H H Ph H H H Me Me 36- 245 Me H H Ph H H H H H H Ph H H Me Me 36- 246 Me H H Ph H H H H H H H Ph H Me Me 36- 247 Me H H Ph H H H H H H H H Ph Me Me 36- 248 Ph H H Ph H H H H H H H H H Me Me 36- 249 Ph H H Ph H H H Me H H H H H Me Me 36- 250 Ph H H Ph H H H H Me H H H H Me Me 36- 251 Ph H H Ph H H H H H Me H H H Me Me 36- 252 Ph H H Ph H H H H H H Me H H Me Me 36- 253 Ph H H Ph H H H H H H H Me H Me Me 36- 254 Ph H H Ph H H H H H H H H Me Me Me 36- 255 Ph H H Ph H H H Ph H H H H H Me Me 36- 256 Ph H H Ph H H H H Ph H H H H Me Me 36- 257 Ph H H Ph H H H H H Ph H H H Me Me 36- 258 Ph H H Ph H H H H H H Ph H H Me Me 36- 259 Ph H H Ph H H H H H H H Ph H Me Me 36- 260 Ph H H Ph H H H H H H H H Ph Me Me
36- 261 Me H H H Ph H H H H H H H H Me Me 36- 262 Me H H H Ph H H Me H H H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 36- 263 Me H H H Ph H H H Me H H H H Me Me 36- 264 Me H H H Ph H H H H Me H H H Me Me 36- 265 Me H H H Ph H H H H H Me H H Me Me 36- 266 Me H H H Ph H H H H H H Me H Me Me 36- 267 Me H H H Ph H H H H H H H Me Me Me 36- 268 Me H H H Ph H H Ph H H H H H Me Me 36- 269 Me H H H Ph H H H Ph H H H H Me Me 36- 270 Me H H H Ph H H H H Ph H H H Me Me 36- 271 Me H H H Ph H H H H H Ph H H Me Me 36- 272 Me H H H Ph H H H H H H Ph H Me Me 36- 273 Me H H H Ph H H H H H H H Ph Me Me 36- 274 Ph H H H Ph H H H H H H H H Me Me 36- 275 Ph H H H Ph H H Me H H H H H Me Me 36- 276 Ph H H H Ph H H H Me H H H H Me Me 36- 277 Ph H H H Ph H H H H Me H H H Me Me 36- 278 Ph H H H Ph H H H H H Me H H Me Me 36- 279 Ph H H H Ph H H H H H H Me H Me Me 36- 280 Ph H H H Ph H H H H H H H Me Me Me 36- 281 Ph H H H Ph H H Ph H H H H H Me Me 36- 282 Ph H H H Ph H H H Ph H H H H Me Me 36- 283 Ph H H H Ph H H H H Ph H H H Me Me 36- 284 Ph H H H Ph H H H H H Ph H H Me Me 36- 285 Ph H H H Ph H H H H H H Ph H Me Me 36- 286 Ph H H H Ph H H H H H H H Ph Me Me
36- 287 Me H H H H Ph H H H H H H H Me Me 36- 288 Me H H H H Ph H Me H H H H H Me Me 36- 289 Me H H H H Ph H H Me H H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 36- 290 Me H H H H Ph H H H Me H H H Me Me 36- 291 Me H H H H Ph H H H H Me H H Me Me 36- 292 Me H H H H Ph H H H H H Me H Me Me 36- 293 Me H H H H Ph H H H H H H Me Me Me 36- 294 Me H H H H Ph H Ph H H H H H Me Me 36- 295 Me H H H H Ph H H Ph H H H H Me Me 36- 296 Me H H H H Ph H H H Ph H H H Me Me 36- 297 Me H H H H Ph H H H H Ph H H Me Me 36- 298 Me H H H H Ph H H H H H Ph H Me Me 36- 299 Me H H H H Ph H H H H H H Ph Me Me 36- 300 Ph H H H H Ph H H H H H H H Me Me 36- 301 Ph H H H H Ph H Me H H H H H Me Me 36- 302 Ph H H H H Ph H H Me H H H H Me Me 36- 303 Ph H H H H Ph H H H Me H H H Me Me 36- 304 Ph H H H H Ph H H H H Me H H Me Me 36- 305 Ph H H H H Ph H H H H H Me H Me Me 36- 306 Ph H H H H Ph H H H H H H Me Me Me 36- 307 Ph H H H H Ph H Ph H H H H H Me Me 36- 308 Ph H H H H Ph H H Ph H H H H Me Me 36- 309 Ph H H H H Ph H H H Ph H H H Me Me 36- 310 Ph H H H H Ph H H H H Ph H H Me Me 36- 311 Ph H H H H Ph H H H H H Ph H Me Me 36- 312 Ph H H H H Ph H H H H H H Ph Me Me
36- 313 Me H H H H H Ph H H H H H H Me Me 36- 314 Me H H H H H Ph Me H H H H H Me Me 36- 315 Me H H H H H Ph H Me H H H H Me Me 36- 316 Me H H H H H Ph H H Me H H H Me Me Cpd No. Rai Ra2 Ra3 Ra4 Ra5 Ra6 Ra7 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 36- 317 Me H H H H H Ph H H H Me H H Me Me 36- 318 Me H H H H H Ph H H H H Me H Me Me 36- 319 Me H H H H H Ph H H H H H Me Me Me 36- 320 Me H H H H H Ph Ph H H H H H Me Me 36- 321 Me H H H H H Ph H Ph H H H H Me Me 36- 322 Me H H H H H Ph H H Ph H H H Me Me 36- 323 Me H H H H H Ph H H H Ph H H Me Me 36- 324 Me H H H H H Ph H H H H Ph H Me Me 36- 325 Me H H H H H Ph H H H H H Ph Me Me 36- 326 Ph H H H H H Ph H H H H H H Me Me 36- 327 Ph H H H H H Ph Me H H H H H Me Me 36- 328 Ph H H H H H Ph H Me H H H H Me Me 36- 329 Ph H H H H H Ph H H Me H H H Me Me 36- 330 Ph H H H H H Ph H H H Me H H Me Me 36- 331 Ph H H H H H Ph H H H H Me H Me Me 36- 332 Ph H H H H H Ph H H H H H Me Me Me 36- 333 Ph H H H H H Ph Ph H H H H H Me Me 36- 334 Ph H H H H H Ph H Ph H H H H Me Me 36- 335 Ph H H H H H Ph H H Ph H H H Me Me 36- 336 Ph H H H H H Ph H H H Ph H H Me Me 36- 337 Ph H H H H H Ph H H H H Ph H Me Me 36- 338 Ph H H H H H Ph H H H H H Ph Me Me
Table 37
Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 ] Rb5 Rb6 Rb7 Rb8
37- 1 Me Me Me H H H H H H Me Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 37-2 Me Me Me Me H H H H H Me Me 37-3 Me Me Me H Me H H H H Me Me 37-4 Me Me Me H H Me H H H Me Me 37-5 Me Me Me H H H Me H H Me Me 37-6 Me Me Me H H H H Me H Me Me 37-7 Me Me Me H H H H H Me Me Me 37-8 Me Me Me Ph H H H H H Me Me 37-9 Me Me Me H Ph H H H H Me Me 37-10 Me Me Me H H Ph H H H Me Me 37- 11 Me Me Me H H H Ph H H Me Me 37- 12 Me Me Me H H H H Ph H Me Me 37- 13 Me Me Me H H H H H Ph Me Me 37-14 Ph Me Me H H H H H H Me Me 37-15 Ph Me Me Me H H H H H Me Me 37-16 Ph Me Me H Me H H H H Me Me 37- 17 Ph Me Me H H Me H H H Me Me 37-18 Ph Me Me H H H Me H H Me Me 37-19 Ph Me Me H H H H Me H Me Me 37-20 Ph Me Me H H H H H Me Me Me 37-21 Ph Me Me Ph H H H H H Me Me 37-22 Ph Me Me H Ph H H H H Me Me 37-23 Ph Me Me H H Ph H H H Me Me 37-24 Ph Me Me H H H Ph H H Me Me 37-25 Ph Me Me H H H H Ph H Me Me 37-26 Ph Me Me H H H H H Ph Me Me
37-27 Me Ph Me H H H H H H Me Me 37-28 Me Ph Me Me H H H H H Me Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 37-29 Me Ph Me H Me H H H H Me Me 37-30 Me Ph Me H H Me H H H Me Me 37-31 Me Ph Me H H H Me H H Me Me 37-32 Me Ph Me H H H H Me H Me Me 37-33 Me Ph Me H H H H H Me Me Me 37-34 Me Ph Me Ph H H H H H Me Me 37-35 Me Ph Me H Ph H H H H Me Me 37-36 Me Ph Me H H Ph H H H Me Me 37-37 Me Ph Me H H H Ph H H Me Me 37-38 Me Ph Me H H H H Ph H Me Me 37-39 Me Ph Me H H H H H Ph Me Me 37-40 Ph Ph Me H H H H H H Me Me 37-41 Ph Ph Me Me H H H H H Me Me 37-42 Ph Ph Me H Me H H H H Me Me 37-43 Ph Ph Me H H Me H H H Me Me 37-44 Ph Ph Me H H H Me H H Me Me 37-45 Ph Ph Me H H H H Me H Me Me 37-46 Ph Ph Me H H H H H Me Me Me 37-47 Ph Ph Me Ph H H H H H Me Me 37-48 Ph Ph Me H Ph H H H H Me Me 37-49 Ph Ph Me H H Ph H H H Me Me 37-50 Ph Ph Me H H H Ph H H Me Me 37-51 Ph Ph Me H H H H Ph H Me Me 37-52 Ph Ph Me H H H H H Ph Me Me
37-53 Me Me Ph H H H H H H Me Me 37-54 Me Me Ph Me H H H H H Me Me 37-55 Me Me Ph H Me H H H H Me Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 37-56 Me Me Ph H H Me H H H Me Me 37-57 Me Me Ph H H H Me H H Me Me 37-58 Me Me Ph H H H H Me H Me Me 37-59 Me Me Ph H H H H H Me Me Me 37-60 Me Me Ph Ph H H H H H Me Me 37-61 Me Me Ph H Ph H H H H Me Me 37-62 Me Me Ph H H Ph H H H Me Me 37-63 Me Me Ph H H H Ph H H Me Me 37-64 Me Me Ph H H H H Ph H Me Me 37-65 Me Me Ph H H H H H Ph Me Me 37-66 Ph Me Ph H H H H H H Me Me 37-67 Ph Me Ph Me H H H H H Me Me 37-68 Ph Me Ph H Me H H H H Me Me 37-69 Ph Me Ph H H Me H H H Me Me 37-70 Ph Me Ph H H H Me H H Me Me 37-71 Ph Me Ph H H H H Me H Me Me 37-72 Ph Me Ph H H H H H Me Me Me 37-73 Ph Me Ph Ph H H H H H Me Me 37-74 Ph Me Ph H Ph H H H H Me Me 37-75 Ph Me Ph H H Ph H H H Me Me 37-76 Ph Me Ph H H H Ph H H Me Me 37-77 Ph Me Ph H H H H Ph H Me Me 37-78 Ph Me Ph H H H H H Ph Me Me
37-79 Me Ph Ph H H H H H H Me Me 37-80 Me Ph Ph Me H H H H H Me Me 37-81 Me Ph Ph H Me H H H H Me Me 37-82 Me Ph Ph H H Me H H H Me Me Cpd No. Rai Ra2 Ra3 Rbl Rb2 Rb3 Rb4 Rb5 Rb6 Rb7 Rb8 37-83 Me Ph Ph H H H Me H H Me Me 37-84 Me Ph Ph H H H H Me H Me Me 37-85 Me Ph Ph H H H H H Me Me Me 37-86 Me Ph Ph Ph H H H H H Me Me 37-87 Me Ph Ph H Ph H H H H Me Me 37-88 Me Ph Ph H H Ph H H H Me Me 37-89 Me Ph Ph H H H Ph H H Me Me 37-90 Me Ph Ph H H H H Ph H Me Me 37-91 Me Ph Ph H H H H H Ph Me Me 37-92 Ph Ph Ph H H H H H H Me Me 37-93 Ph Ph Ph Me H H H H H Me Me 37-94 Ph Ph Ph H Me H H H H Me Me 37-95 Ph Ph Ph H H Me H H H Me Me 37-96 Ph Ph Ph H H H Me H H Me Me 37-97 Ph Ph Ph H H H H Me H Me Me 37-98 Ph Ph Ph H H H H H Me Me Me 37-99 Ph Ph Ph Ph H H H H H Me Me 37- 100 Ph Ph Ph H Ph H H H H Me Me 37- 101 Ph Ph Ph H H Ph H H H Me Me 37- 102 Ph Ph Ph H H H Ph H H Me Me 37- 103 Ph Ph Ph H H H H Ph H Me Me 37- 104 Ph Ph Ph H H H H H Ph Me Me
Table 38. "A" part of ligand
Figure imgf000366_0001
Figure imgf000367_0001
Figure imgf000368_0001
Figure imgf000368_0002
Figure imgf000368_0003
Figure imgf000368_0005
Figure imgf000368_0004
Figure imgf000369_0001
Table 39. "B" part of ligand
Figure imgf000369_0002
Figure imgf000370_0001
Figure imgf000371_0001
Figure imgf000371_0002
Figure imgf000371_0003
Figure imgf000371_0005
Figure imgf000371_0006
Figure imgf000371_0004
Figure imgf000372_0001
Figure imgf000373_0001
Table 40. "C" Ligands
Figure imgf000373_0002
Table 41. Preferred compounds
Figure imgf000374_0001
Figure imgf000375_0001
Figure imgf000376_0001
Figure imgf000377_0001
Figure imgf000379_0001
Figure imgf000380_0001
Figure imgf000381_0001
Figure imgf000382_0001
Figure imgf000383_0001
Figure imgf000384_0001
Figure imgf000385_0001
Figure imgf000386_0001
Figure imgf000387_0001
[0478] It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. It is understood that various theories as to why the invention works are not intended to be limiting. For example, theories relating to charge transfer are not intended to be limiting.
Material Definitions: [0479] As used herein, abbreviations refer to materials as follows: CBP: 4,4'-N,N-dicarbazole-biphenyl m-MTDATA 4,4',4"-tris(3-methylphenylphenlyamino)triphenylamine Alq3: 8-tris-hydroxyquinoline aluminum Bphen: 4,7-diphenyl- 1 , 10-phenanthroline n-BPhen: n-doped BPhen (doped with lithium) F4-TCNQ: tetrafluoro-tetracyano-quinodimethane p-MTDATA: p-doped m-MTDATA (doped with F4-TCNQ) Ir(ρρy)3: tris(2-phenylpyridine)-iridium Ir(ppz)3: tris(l-phenylpyrazoloto,N,C(2')iridium(III) BCP: 2,9-dimethyl-4,7-diphenyl- 1 , 10-phenanthroline TAZ: 3 -phenyl-4-( 1 '-naphthyl)-5-phenyl- 1 ,2,4-triazole CuPc: copper phthalocyanine. ITO: indium tin oxide
NPD: N,N' -diphenyl-N-N' -di( 1 -naρhthyl)-benzidine
TPD: N,N' -diphenyl-N-N' -di(3 -toly)-benzidine
BAlq: aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate mCP: 1 ,3-N,N-dicarbazole-benzene
DCM: 4-(dicyanoethylene)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyran
DMQA: N,N' -dimethylquinacridone
PEDOT:PSS : an aqueous dispersion of poly(3,4-ethylenedioxythiophene) with polystyrenesulfonate (PSS)
UGH 1 ,3-bis(triphenylsilyl)benzene l-Ph-3-Me-imid 1 -phenyl-3 -methyl-imidazolin-2-ylidene- C, C2 1 -Ph-3-Me-benzimid fac-iridium(III) tris( 1 -phenyl-3 -methyl-benzimidazolin- 2-ylidene-C,A') mer-(F ppz) Ir( 1 -Ph-3 -Me-imid) mer-iridium(III) bis[(2-(4',6' -difluorophenyl)-2- pyrazolinato-N, C2 )] ( 1 -phenyl-3 -methyl-imidazolin-2- ylidene- C2') mer-(2-(tpy)2Ir( 1 -Ph-3 -Me-imid) mer-iridium(III) bis[(2-(4'-methylphenyl)-2-pyridinato- N, C2')] ( 1 -phenyl-3 -methyl-imidazolin-2-ylidene- C, C2 ' fac-(2-(tpy)2Ir(l-Ph-3-Me-imid) fac-iridium(III) bis[(2-(4'-methylphenyl)-2-pyridinato- NC2')] (1 -phenyl-3 -methyl-imidazolin^-ylidene- 2 )
[(l-Ph-3-Me-imid)2IrCl]2 Iridium(III) bis( 1 -phenyl-3 -methyl-imidazolin-2- ylidene- C,Cf ) chloride
(1 -Ph-3-Me-imid)2Ir(t-Bu-bpy)+ Iridium(III) bis[(l-phenyl-3-methyl-imidazolin-2- ylidene-C,<A)] (4,4'-di-tert-butyl-(2,2')biρyridinyl) mer-Ir( 1 -Ph-3 -Me-imid)3 mer-iridium(III) tris(l -phenyl-3 -methyl-imidazolin-2- ylidene-C, C2 )
(Ir-Fl-Me-imid)3 tris(l-(2'-(9',9'-dimethyl)fluorenyl)-3-methyl- imidazolin-2-ylidene-C,C3 ') iridium(III) Ir(4,6-F ρρy)3: tris[2-(4,6-difluorophenyl)pyridine]iridium(III)
EXPERIMENTAL:
[00103] Specific representative embodiments of the invention will now be described, including how such embodiments may be made. It is understood that the specific methods, materials, conditions, process parameters, apparatus and the like do not necessarily limit the scope of the invention.
Synthesis of imidazolate carbene precursors
[0480] 1-Phenylimidazole was purchased from Aldrich. All other aryl imidazoles were prepared by a modified UUmann coupling reaction between imidazoie or benzimidazole and the appropriate aryl iodide in anhydrous N,N-dimethylformamide using a CuI/1,10- phenanthroline catalyst and Cs2CO3 base, as described in Klapars, et al, J. Am. Chem. Soc, 2001, 123; 7727-7729. The carbene precursor imidazolates were prepared by methylating the corresponding imidazoles with excess methyl iodide in toluene.
Example 1: Synthesis l-phenyl-3-methylimidazolate iodide
[0481] 1 -phenyl-3 -methylimidazolate iodide was synthesized using the modified
UUmann coupling reaction described above. !H NMR (250 MHz, CDC13), ppm: 10.28 (s, 1H), 7.77-7.70 (m, 4H), 7.56-7.46 (m, 3H), 4.21 (s, 3H).
Example 2: Synthesis of l-Phenyl-3-methyl-benzimidazolate iodide
[0482] In the dark, an oven-dried 50 ml round-bottomed flask containing a stir bar was charged with Cul (0.171 g, 0.1 eq.), benzimidazole (1.273 g, 1.2 eq.), and cesium carbonate (6.138 g, 2.1 eq.) respectively. The round-bottomed flask with the contents was sealed with septa and degassed with argon for 15 minutes. Iodobenzene (1ml, 1 eq.), 1,10- Phenanthroline (0.323 g, 0.2 eq.), and dimethylformamide (25 ml) were then successively added into the round-bottomed flask under a continuous flow of argon. The reaction mixture was degassed with argon for 30 minutes. The reaction was stirred with heating via an oil bath at 110°C for 24 hours in the dark under nitrogen. The reaction mixture was cooled to ambient temperature and concentrated in vacuo. 10 ml of ethyl acetate was added into the concentrated reaction mixture. It was then filtered and washed with 30 ml of ethyl acetate. The filtrate was concentrated under vacuo to give the crude product. The crude product was purified by column chromatography on silica gel (40% ethyl acetate: 60% hexane as the eluent) providing 0.780 g of 1 -Phenyl benzoimidazole (45% yield) as yellow liquid. [0483] Methyl iodide (0.550 ml, 2.2 eq.) was syringed into a 25 ml round-bottomed flask charged with 1-phenyl benzoimidazole (0.780 g, 1 eq.) and toluene (15 ml). The reaction was stirred and heated at 30°C for 24 hours. The white precipitate was filtered and washed with 20 ml of toluene. The white precipitate was air-dried and weighed to give 0.725 g of 1 -phenyl-3 -methyl-benzimidizolate iodide (54% yield).
Synthesis of Iridium imidazoie carbene complexes
Example 3: Synthesis of mer-iridium(III) bis[(2-(4',6'-difluorophenyl)-2-pyrazolinato- N,C2')] (l-phenyl-3-methyl-imidazolin-2-yUdene-C,C^')
[0484] A 25 ml round-bottomed flask was charged with 0.014 g of silver(I) oxide,
0.030 g of 1 -ρhenyl-3 -methyl-imidazolate iodide, 0.062 g of [(F2ρpz)2IrCl]2, and 15 ml of 1,2-dichloroethane. The reaction was stirred and heated with an oil bath at 77°C for 15 hours in the dark under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure. Filtration through Celite using dichloromethane as the eluent was performed to remove the silver(I) salts. A light yellow solution was obtained and addition of methanol gave 0.025 g (30% yield) of iridium complex as a colorless solid. 1H NMR (500 MHz, CDC13), ppm: 8.24 (d, IH, J= 2.8 Hz), 8.16 (d, IH, J= 2.8 Hz), 7.43 (d, IH, J= 1.9 Hz), 7.15 (d, IH, J= 7.5 Hz), 6.96 (ddd, IH, J= 7.5, 7.0, 1.9 Hz), 6.93 (dd, IH, J= 7.0, 1.9 Hz), 6.82 (m, 2H), 6.78 (d, IH, J= 1.9 Hz), 6.47 (ddd, IH, J= 11.7, 8.4, 2.3 Hz), 6.43 (ddd, IH, J= 11.7, 8.4, 2.3 Hz), 6.29 (t, IH, J= 2.3 Hz), 6.28 (t, IH, J= 2.3 Hz), 6.14 (dd, IH, J= 7.5, 2.3 Hz), 5.85 (dd, IH, J= 8.0, 2.3 Hz), 3.29 (s, 3H). Fig. 3 shows the 1H NMR spectra of mer-(F2ppz)2Ir(l-Ph-3-Me-imid) in CDC13.
Example 4: Synthesis of mer-iridium(III) bis[(2-(4'-methylphenyl)-2-pyridinato- N,<^')] (l-phenyl-3-methyl-iιm^azolin-2-yUdene-C,(A)
[0485] A 50 ml round-bottomed flask was charged with 0.103 g of silver(I) oxide,
0.118 g of l-phenyl-3-methyl-imidazolate iodide, 0.168 g of [(tpy) IrCl]2, and 25 ml of 1,2- dichloroethane. The reaction was stirred and heated with an oil bath at 77°C for 15 hours in the dark under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure. Filtration through Celite using dichloromethane as the eluent was performed to remove the silver(I) salts. A yellow solution was obtained and further purified by flash column chromatography on silica gel using dichloromethane as the eluent that was reduced in volume to ca. 2 ml. Addition of methanol gave 0.121 g (59% yield) of iridium complex as a bright yellow solid. [0486] Fig. 4 shows the 1H NMR spectra of mer-(tρy)2Ir(l -Ph-3-Me-imid) in CDC13.
Fig. 6 shows the plot of current (μA) vs. voltage (V) of a mer-(tpy)2Ir(l -Ph-3 -Me-imid) compound with ferrocene as an internal reference. A solvent of DMF with 0.1M B^ ^PFδ " is used. Fig. 9 shows the emission spectra of mer-(tpy)2Ir(l-Ph-3-Me-imid) in 2-MeTHF at room temperature and at 77K. The compound exhibits lifetimes of 1.7 μs at room temperature and 3.3 μs at 77K. Example 5: Synthesis of fac-iridium(III) bis[(2-(4'-methylphenyl)-2-pyridinato-iV, 2')] (l-phenyl-3-methyl-imidazolin-2-ylidene-C,C2 )
[0487] A 200 ml quartz flask was charged with 0.0.059 g of mer-(tpy)2Ir(l-Ph-3-Me- imid) and 50 ml of acetonitrile and sparged with nitrogen for five minutes. The mixture was photolyzed for 63 hours using 254 nm light. After photolysis the solvent was removed under reduced pressure and the yellow solid was taken up in 2 ml dichloromethane. Addition of methanol gave 0.045 g (75% yield) of iridium complex as a bright yellow solid that was collected by centrifuge.
[0488] Fig. 5 shows the 1H NMR spectra of fac-(tpy)2Ir(l -Ph-3 -Me-imid) in CDC13.
Fig. 7 shows the plot of current (μA) vs. voltage (V) of a fac-(tpy)2Ir(l -Ph-3 -Me-imid) compound with ferrocene as an internal reference. A solvent of DMF with 0.1M Bx^NT'Fό" is used. Fig. 8 shows the absorption spectra of fac-(tpy)2Ir(l-Ph-3-Me-imid) and mer- (tpy)2Ir(l -Ph-3 -Me-imid) in CH2C1 . Fig. 10 shows the emission spectra of fac-(tpy) Ir(l-Ph- 3 -Me-imid) in 2-MeTHF at room temperature and at 77K. The compound exhibits lifetimes of 1.7 μs at room temperature and 3.3 μs at 77K.
Example 6: Synthesis of Iridium(III) bis(l-phenyl-3-methyl-imidazolin-2-ylidene- C,Cf ) chloride dimer
[0489] A 100 ml round-bottomed flask was charged with 0.428 g of silver(I) oxide,
0.946 g of 1 -phenyl-3 -methyl-imidazolate iodide, 0.301 g of iridium trichloride hydrate, and 60 ml of 2-ethoxyethanol. The reaction was stirred and heated with an oil bath at 120°C for 15 hours under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and the solvent was removed under reduced pressure. The black mixture was extracted with ca. 20 ml dichloromethane and the extract was reduced to ca. 2 ml volume. Addition of methanol gave 0.0160 g (30% yield) of the iridium dimer complex as an off-white solid. [0490] Fig. 11 shows the 1H NMR spectra of [(1 -Ph-3-Me-imid)2rrCl]2 in CDC13.
Example 7: Synthesis of mer-iridium(III) tris(l-phenyl-3-methyl-imidazolin-2- ylidene-Cj 2 )
[0491] A 50 ml round-bottomed flask was charged with 0.076 g of silver(I) oxide,
0.109 g of 1 -phenyl-3 -methyl-imidazolate iodide, 0.029 g of iridium trichloride hydrate, and 20 ml of 2-ethoxyethanol. The reaction was stirred and heated with an oil bath at 120°C for 15 hours under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure. Filtration through Celite using dichloromethane as the eluent was performed to remove the silver(I) salts. A white solid was obtained after removing the solvent in vacuo and was washed with methanol to give 0.016 g (24% yield) of meridional tris-iridium complex as a white solid. [0492] Fig. 15 shows the 1H NMR spectra of mer-Ir(l-Ph-3-Me-imid)3 in CDC13. Fig.
16 shows the 13C NMR spectra of mer-Ir(l-Ph-3-Me-imid)3 in CDC13. Fig. 17 shows the plot of current (μA) vs. voltage (V) of a mer-Ir(l-Ph-3-Me-imid) compound with ferrocene as an internal reference. A solvent of DMF with 0.1M Bu4N+PF6 " is used. Fig. 18 shows the emission spectra of mer-Ir(l-Ph-3-Me-imid)3 in 2-MeTHF at room temperature and at 77K.
Example 8: Synthesis of f ac-iridium(III) tris(l-phenyl-3-methyl-imidazolin-2-ylidene-
C,C2')
[0493] A 50 ml round-bottomed flask was charged with 0.278 g of silver(I) oxide,
0.080 g of l-phenyl-3-methyl-imidazolate iodide, 0.108 g of [(l-Ph-3-Me-imid)2IrCl]2, and 25 ml of 1,2-dichloroethane. The reaction was stirred and heated with an oil bath at 77°C for 15 hours under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure. Filtration through Celite using dichloromethane as the eluent was performed to remove the silver(I) salts. A light brown solution was obtained and further purified by flash column chromatography on silica gel using dichloromethane as the eluent and was then reduced in volume to ca. 2 ml. Addition of methanol gave 0.010 g (8% yield) of iridium complex as a colorless solid.
[0494] Fig. 19 shows the 1H NMR spectra of fac-Ir(l -Ph-3-Me-imid)3 in CDC13. Fig.
20 shows the absorption spectra of fac-Ir(l-Ph-3-Me-imid)3 in CH2C12. Fig. 21 shows the emission spectra of fac-Ir(l-Ph-3-Me-imid) in 2-MeTHF at room temperature and at 77K. The compound exhibits lifetimes of 0.50 μs at room temperature and 6.8 μs at 77K.
Example 9: Synthesis of fac-iridium(III) tris(l-phenyl-3-methyl-benzimidazolin-2- ylidene-CjC2 )
[0495] A 25 ml round-bottomed flask was charged with 0.165 g of silver(I) oxide,
0.200 g of 1 -phenyl-3 -methyl-benzimidazolate iodide, 0.0592 g of iridium trichloride hydrate, and 15 ml of 2-ethoxyethanol. The reaction was stirred and heated with an oil bath at 120°C for 24 hours under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure. Flash column chromatography on Celite using dichloromethane as the eluent was performed to remove the silver(I) salts. A brown oil was obtained and further purified by flash column chromatography on silica gel using dichloromethane as the eluent to give 0.050 g of facial tris-iridium complex (33% yield) as an off-white solid.
[0496] Fig. 22 shows the 1H NMR spectra of 1 -Ph-3-Me-benzimid in CDC13. Fig. 23 shows the 1H NMR spectra of fac-fr(l-Ph-3-Me-benzimid)3 in CDC13. Fig. 24 shows the plot of current (mA) vs. voltage (V) of a fac-Ir(l-Ph-3-Me-benzimid)3 compound with ferrocene as an internal reference. A solvent of anhydrous DMF is used. Fig. 25 shows the emission spectra of fac-Ir(l-Ph-3-Me-benzimid)3 in 2-MeTHF at room temperature and at 77K. The compound emits a spectrum at CIE 0.17, 0.04. The lifetime measurements of an Ir(l-Ph-3- Me-benzimid)3 compound is shown on Table A.
Table A Temperature Peak wavelength Lifetime, τ
Room temperature 402 nm 0.32 μs Room temperature 420 nm 0.29 μs 77 K 400 nm 2.6 μs 77 K 420 nm 2.7 μs
Example 10: Synthesis of iridium(III) bis(l-phenyl-3-methyl-imidazolin-2-ylidene- C,C2') (4,4'-di-tert-butylbipyidyl) hexafluorophosphate
[0497] A 25 ml round-bottomed flask was charged with 0.010 g of [(l-Ph-3-Me- imid)2IrCl]2, 0.005 g of 4'4'-di-tert-butyl-bipyridine and 15 ml of dichloromethane. The reaction was stirred at room temperature for 16 hours. The solvent was removed under reduced pressure and the resultant yellow solid was dissolved in ca. 2 ml methanol. Addition of an aqueous ammonium hexafluorophosphate solution produced a yellow precipitate. The precipitate was collected by filtration, washed with water and dried. Chromatography on silica addition of hexanes gave 0.015 g (82%) yield) of iridium complex as an orange solid. [0498] Fig. 12 shows the 1H NMR spectra of (l-Ph-3-Me-imid)2Ir(t-Bu-bpy)+ in
CDC13. Fig. 13 shows the absorption spectra of (l-Ph-3-Me-imid)2Ir(t-Bu-bpy)+ in CH2C12. Fig. 14 shows the emission spectra of (l-Ph-3-Me-imid)2Ir(t-Bu-bpy)+ in 2-MeTHF at 77K and (l-Ph-3-Me-imid)2Ir(t-Bu-bpy)+ in CH2C12 at room temperature. The compound exhibits lifetimes of 0.70 μs at room temperature and 6.0 μs at 77K.
Example 11: Synthesis of mer-iridium(III) bis[(2-(5'-biphenyl)-2-pyridinato-N, 2')] (1- phenyl-3-methyl-imidazolin-2-ylidene- C^C2
[0499] Step 1: Synthesis of 1 -phenyl-3 -methylimidozolate iodide
About 13 g of 1-phenylimidazole and 13 g of methyl iodide were added to 100 ml of toluene and heated to a gentle reflux. After 4 hours, the solvent was removed and the product was precipitated from dichloromethane with diethyl ether. The white solid product was collected by vacuum filtration yielding about 20 g of 1 -phenyl-3 -methylimidozolate iodide. [0500] Step 2:
To a 500 ml round bottom flasks 4.2 grams of 1 -phenyl-3 -methylimidozolate iodide, 5 g of [IrCl{2-(5-biphenyl)-pyridine} ] , made by methods described in Thompson, M.E., J. Am. Chem. Soc, 2001, 123,4304-4312, 3.4 grams of silver oxide, and 200 ml of 1,2- dicholorethane were added. This mixture was heated to reflux for 5 hours under a nitrogen atmosphere. The reaction was allowed to cool and was then filtered through silica gel using dichloromethane as the eluent. The good fractions were combined, the solvent was removed, and the product was crystallized from a dichloromethane/hexane mixture to yield mer- iridium(III) bis[(2-(5'-biphenyl)-2-pyridinato-N,C2)] (1 -phenyl-3 -methyl-imidazolin-2- ylidene- C, ) as a yellow solid.
Figure imgf000394_0001
Example 12: Synthesis of fac-iridium(III) bis[(2-(5,-biphenyl)-2-pyridinato-N, 2')] (1- phenyl-3-methyl-imidazolin-2-ylidene-C,C2 )
[0501] Step l :
Mer-iridium(III) bis[(2-(5,-biphenyl)-2-pyridinato-N>C2)] (1 -phenyl-3 -methyl-imidazolin-2- ylidene- 2 ) was synthesized as described in Example 10 above.
[0502] Step 2:
2 g of mer-iridium(III) bis[(2-(5'-biphenyl)-2-pyridinato-N, 2')] (1 -phenyl-3 -methyl- imidazolin-2-ylidene-C, C2 ) solid was dissolved in acetonitrile, placed in a quartz reaction flask, and exposed to ultraviolet radiation in a Rayonet Photochemical Reactor for 18 hours. Most of the solvent was removed by rotoevaporation and the solids were filtered. The product was recrystallized form dichloromethane/methanol. Approximately 1.2 g of solids were collected by vacuum filtration. The obtained fac-iridium(III) bis[(2-(5'-biphenyl)-2- pyridinato-NC2')] ( 1 -phenyl-3 -methyl-imidazolin-2-ylidene-C,C2 ) was further purified by sublimation.
Example 13: Synthesis of mer-iridium(III) tris [l,(2-iodo-9,9-dimethylfluorenyl)-3- methyl-benzimidazolin-2-ylidene-C,C and fac-iridium(III) tris [l,(2-iodo-9,9- dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C2
[0503] Step 1 : Synthesis of 2-Iodofluorene
A 250 mL round-bottomed flask was charged with 20.0g (120 mmol) fluorene, 16.0g (60 mmol) iodine and 4.0g (17 mmol) periodic acid. 150mL (80 %) acetic acid was added to the reaction mixture. The mixture was stirred under nitrogen at 80°C for 4 hours. The mixture was then allowed to cool to ambient temperature. The solid residue was vacuum filtered, dissolved in toluene and then washed with 5% sodium hydrogen sulphite(to remove excess iodine). The toluene solution was concentrated under vacuo and then passed through a flash column using toluene as the eluent to give 32.0 g (91 % yield) of the product (off white solid).
Figure imgf000395_0001
[0504] Step 2: Synthesis of 2-iodo-9,9-dimethyl-fluorene
A 500 mL round bottomed flask was charged with 21.8 g (70 mmol) 2-Iodofluorene and 1.18 g (5 mmol) benzyltriethylammonium chloride. 200 mL of dimethylsulfoxide (DMSO) was then added followed by 28 mL (50%) NaOH. The mixture was allowed to stir under nitrogen for 1 hour, before 29 g (210 mmol) methyl iodide was added through the septum. The mixture was allowed to stir at room temperature for 18 hours. After cooling to ambient temperature the mixture was transferred to a 1 L separatory funnel. 100 mL of water and 100 mL of diethylether were added to the mixture. The organic layer was collected and the aqueous layer was extracted with diethyl ether (4 x 100 mL). The organic fractions were combined, dried over anhydrous magnesium sulfate, and the solvent evaporated under vacuo. A flash column was then performed using hexanes as the eluent to give 21.0 g (88% yield) of the product (yellow oil).
Figure imgf000396_0001
[0505] Step 3: Synthesis of l,(2-iodo-9,9-dimethylfluorenyl)benzimidazole
A three neck 250 mL round bottomed flask was charged with 8.42 g (1.2 molar equivalent) benzimidazole, 2.13 g (20 mol%) 1,10-phenanthroline and 40.6 g (2.1 molar equivalent) cesium carbonate. Argon was then allowed to flow over the material for about 10 mins. While Argon was still flowing, 1.12 g (10 mol%) copper iodide was added to the mixture in the dark. The three-neck flask was covered with aluminum foil to protect the reaction mixture from light. 19 g (30 mmol) 2-iodo-9,9-dimethyl-fluorene, was dissolved in 20mL of anhydrous dimethylformamide (DMF) and added to the mixture via a syringe through the septum. 20 mL of DMF was then further added to allow the mixture to stir. The reaction mixture was heated to 110°C for 48 hours. After cooling, the mixture was filtered using vacuum filtration. The residue was washed with ethyl acetate and the filtrate concentrated under vacuo. A flash column was performed using hexanes (to get rid of any unreacted 2- iodo-9,9-dimethyl-fluorene, the product stayed in the column). Following the hexanes, a new receiving flask was placed under the column and the eluent was changed to ethylacetate to give the product 12.0 g (66% yield) of product.
Figure imgf000396_0002
[0506] Step 4: Synthesis of [1, (2-iodo-9,9-dimethylfluorenyl)-3-methyl- benzimidazolatejiodide
[0507] 2.3 mL (34 mmol) methyl iodide was syringed into a 250 mL round-bottomed flask charged with 5 g (16 mmol) l,(2-iodo-9,9-dimethylfluorenyl)benzimidazole and 50 mL toluene. The reaction was stirred and heated to 30°C for 24 hours. The white precipitate was filtered and washed with toluene to give 7.0 g (99% yield) of product.
Figure imgf000397_0001
[0508] Step 5: Synthesis of mer-iridium(III) tris[l,(2-iodo-9,9-dimethylfluorenyl)-3- methyl-benzimidazolin-2-ylidene-C,C2 and fac-iridium(III) tris[l,(2-iodo-9,9- dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C
A 250 mL round-bottomed flask was charged with 1.53 g (11 mmol) silver(I) oxide, 5.0 g (11 mmol) [l,(2-iodo-9,9-dimethylfluorenyl)-3-methyl-benzimidazolate]iodide and 0.66 g (3.6 mmol) iridium(III)trichloride hydrate and 100 mL of dichloroethane. The reaction was stirred and heated at 80°C for 24 hours under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure. Flash column chromatography on silica gel using dichloromethane as the eluent was done to give a 1.9 g (45%yield) of a 70/30 ratio of the mer/fac isomers of the tris Ir(III) product.
Figure imgf000397_0002
Separation of the fac and mer isomers was accomplished by column chromatography using 50/50 ethylacetate and hexanes as the eluent.
Example 14: Synthesis of 3:1 mixture of mer:fac-iridium(III) tris [1,(9,9- dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C2 [0509] Step 1 and Step 2: Same as Example 13
[0510] Step 3: Synthesis of l,(9,9-dimethylfluorenyl)imidazole
A three neck 250 mL round bottomed flask was charged with 5.10g (1.2 molar equivalent) imidazoie, 2.13 g (20 mol%) 1,10-phenanthroline and 40.6 g (2.1 molar equivalent) cesium carbonate. Argon was then allowed to flow over the material for about 10 mins. While Argon was still flowing, 1.12 g (10 mol%) copper iodide was added to the mixture in the dark. The three-neck flask was covered with aluminum foil to protect the reaction mixture from light. 20.0 g (62 mmol) 2-iodo-9,9-dimethyl-fluorene, was dissolved in 20mL of anhydrous dimethylformamide (DMF) and added to the mixture via a syringe through the septum. 20 mL of DMF was then further added to allow the mixture to stir. The reaction mixture was heated to 110°C for 48 hours. After cooling, the mixture was filtered using vacuum filtration. The residue was washed with ethyl acetate and the filtrate concentrated under vacuo. A flash column was performed using hexanes (to get rid of any unreacted 2-iodo-9,9-dimethyl- fluorene, the product stayed in the column). Following the hexanes, a new receiving flask was placed under the column and the eluent was changed to ethylacetate to give the product 10.0 g (62% yield) of product.
Figure imgf000398_0001
[0511] Step 4: Synthesis of [l,(9,9-dimethylfluorenyl)-3-methyl-imidazolate]iodide
2.3 mL (34 mmol) methyl iodide was syringed into a 250 mL round-bottomed flask charged with 5 g (16 mmol) l,(9,9-dimethylfluorenyl)imidazole and 50 mL toluene. The reaction was stirred and heated to 30°C for 24 hours. The white precipitate was filtered and washed with toluene to give 7.0 g (99% yield) of product.
Figure imgf000399_0001
[0512] Step 5: Synthesis of 3:1 mixture of mer:fac-iridium(III) tris [1,(9,9- dimethylfluorenyl)-3-methyl-imidazolin-2-ylidene-C,C2 . A 250 mL round-bottomed flask was charged with 1.53 g (11 mmol) silver(I) oxide, 5.0 g (11 mmol) [1,(9,9- dimethylfluorenyl)-3-methyl-imidazolate]iodide and 0.66 g (3.6 mmol) iridium(III)trichloride hydrate and 100 mL of 2-ethoxyethanol. The reaction was stirred and heated at 80°C for 24 hours under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure. Flash column chromatography on silica gel using dichloromethane as the eluent was done to give a 1.7 g (42%yield) of a 3:1 ratio of the mer/fac isomers of the tris Ir(III) product.
Figure imgf000399_0002
3:1 meπfnc isomers
Example 15: Synthesis of f ac-iridium(III) tris(n-[p-trimethylsilylphenyl]-2-methyl- benzimidazole)
[0513] Step 1: Synthesis of N-(p-trimethylsilylphenyl)benzimidazoleTo a IL 3-neck flask equipped with a mechanical stir arm was added 14.5g (65.1mmol) of l-bromo-4- trimethylsilylbenzene, 9.2g (78.1mmol) of benzimidazole, 9.1g (143mmol) of copper power, 31.4g (228mmol) of potassium carbonate, and 1.7g (6.5mmol) of 18-crown-6. These chemicals were stirred vigorously in 400mL tetrahydronaphthalene at 180 °C under N atmosphere. After 20 hours of heating, the mixture was filtered warm. The solids on the funnel were repeatedly washed with dichloromethane to remove all organic products as filtrate. The mother liquor was then evaporated in vacuo and pooled with a small batch of crude material from a previous reaction. This residue was purified by distilling on a Kugelrohr apparatus twice. At 160 °C, the removal of organic impurities was evidenced. At 200°C the product distilled. Purification gave 14.2g N-(p- trimethylsilylphenyl)benzimidazole as a white solid.
[0514] ■ Step 2: Methylation ofN-(p-trimethylsilylphenyl)benzimidazole
14.1g (52.9 mmol) of N-(ρ-trimethylsilylphenyl)benzimidazole was solubilized with 200mL of toluene in a 500mL flask equipped with a stir bar. To the stirred solution was carefully added 22.5g (159mmol) iodomethane and then was allowed to reflux for 2 hours. Next, the condenser was removed and the flask enriched with lOOmL toluene. A stream of N2 was then passed over the flask to remove excess iodomethane. After the volume of the solution was reduced by half, it was cooled and the white solids collected on a filter and rinsed with toluene followed by hexanes. 20.8g N-(p-trimethylsilylphenyl)benzimidazole was achieved after drying in vacuo (96.3% yield).
[0515] Step 3: Synthesis of fac-iridium(III) tris(n-[p-trimethylsilylphenyl]-2-methyl- benzimidazole)
20mL 2-methoxyethanol was purged with N2 and refluxed in a lOOmL round bottom flask equipped with a stir bar. After deoxygenation of the solvent, the flask was cooled and 1.0g (2.45mmol) N-(ρ-trimethylsilylphenyl)benzimidazole was added along with 0.29g (0.29mmol) IrCl ' 3H2O and 0.76g (3.27mmol) silver(I) oxide. The mixture was refluxed for 2 hours under a stream of N2. The reaction mixture was cooled and the solvent evaporated in vacuo. This residue was dissolved in a minimal amount of dichloromethane and purified on a silica gel column using dichloromethane as eluent. The product fractions were evaporated of solvent and recrystallized from methylene chloride/methanol to give 0.14g fac-iridium(III) tris(n-[p-trimethylsilylphenyl]-2-methyl-benzimidazole) as pale-grey solids (MS confirmed)
Examples 16, 17: Synthesis of fac(mer)-iridium(III) tris(n-[3-biphenyl]-2-methyl- benzimidazole) [Dopant E, F]
[0516] Step 1: Synthesis of N-(3-biphenyl)benzimidazole
To a 3L 3-neck flask equipped with a mechanical stir arm was added lOOg (429 mmol) of 3- bromobiphenyl, 60.7g (514 mmol) of benzimidazole, 60g (943mmol) of copper powder, 207g (1500mmol) of potassium carbonate and 11.3g (42.9mmol) of 18-crown-6. These chemicals were stirred vigorously in -1.5L tetrahydronaphthalene at 180 °C under N2 atmosphere. After 48 hours of heating, the mixture was filtered warm. The solids on the funnel were repeatedly washed with dichloromethane to remove all organic products as filtrate. The mother liquor was then evaporated in vacuo to give a dark residue that was solubilized with a minimal amount of dichloromethane and purified on a silica gel column using a gradient of 50% EtOAc/hexanes -» 100% EtOAc. The purest fractions were evaporated of solvent, and the resultant solids sonciated in hexanes, filtered, washed with hexanes and dried to give 74g N-(3-biphenyl)benzimidazole as off-white solids (64% yield).
[0517] Step 2: Methylation of N-(3-biphenyl)-benzimidazole
74g (274mmol) of N-(3-biphenyl)benzimidazole was solubilized with 400mL of toluene in a IL flask equipped with a stir bar. To the stirred solution was carefully added 117g (821 mmol) iodomethane and then was allowed to reflux for 2 hours. Next, the condenser was removed and the flask enriched with 200mL toluene. A stream of N2 was then passed over the flask to remove excess iodomethane. After the volume of the solution was reduced by half, it was cooled and the white solids collected on a filter and rinsed with toluene followed by hexanes. 108g N-(3-biphenyl)-2-methylbenzimidazole was achieved after drying in vacuo (95.6% yield).
[0518] Step 3: Synthesis of/ac(merAridium(III) tris(n-[3-biphenyl]-2-methyl- benzimidazole)
200mL 2-methoxyethanol was purged with N2 and refluxed in a 500mL round bottom flask equipped with a stir bar. After deoxygenation of the solvent, the flask was cooled and lO.Og (24.3mmol) N-(3-biphenyl)-2-methylbenzimidazole was added along with 2.18g (6.06mmol) IrCl3 ' 3H2O and 4.2g (18.2mmol) silver(I) oxide. The mixture was refluxed for 30 minutes whereupon an additional 4.2g (18.2mmol) silver(I) oxide was added. After heating for an additional 1.5 hours at reflux, HPLC indicated favorable formation of both the mer and fac isomers (~1:2 ratio). The reaction mixture was cooled, enriched with lOOmL dichloromethane and filtered. Whereas the filtrate was put to the side (mer-rich), the resulting solids were removed the filter, stirred vigorously in 500mL MeCl2 and filtered again. This process was performed a second time and the IL of dichloromethane filtrates were evaporated of solvent to give beige solids that were lx recrystallized from dichloromethane/methanol giving 0.95g fac-iridium(III) tris(n- [3 -biphenyl] -2-methyl- benzimidazole) as off-white solids. This material was sublimed in vacuo and afforded 0.23g to be tested in an OLED device (99.5% HPLC assay, 1HNMR confirmed). The mer-rich filtrate was evaporated of solvent and the residue solubilized in dichloromethane and purified on a column of silica using dichloromethane as eluent. The mer-rich fractions were evaporated of solvent and recrystallized from acetonitrile to give ~1.0g 4:1 mer/fac iridιum(III) tris(n-[3-biphenyl]-2-methyl-benzimidazole) as an off-white solid that could not be sublimed (!H NMR confirmed).
Examples 18, 19: Synthesis of fac(mer)-iridium(III) tris(l-(N-[2-methylbenzimidazole])- 4-(o-tolyl)benzene) [Dopant G]
[0519] Step 1 : Synthesis of l-(N-benzimidazole)-4-(o-tolyl)benzene
To a 2L 3-neck flask equipped with a mechanical stir arm was added 46.6g (189 mmol) of 1- bromo-4-(o-tolyl)benzene, 26.7 (226 mmol) of benzimidazole, 26.3g (415mmol) of copper powder, 91. Ig (660mmol) of potassium carbonate and 5.0g (18.9mmol) of 18-crown-6. These chemicals were stirred vigorously in ~1.0L tetrahydronaphthalene at 180 °C under N2 atmosphere. After 48 hours of heating, the mixture was filtered warm. The solids on the funnel were repeatedly washed with dichloromethane to remove all organic products as filtrate. The mother liquor was then evaporated in vacuo to give a dark residue that was solubilized with a minimal amount of dichloromethane and purified on a silica gel column using a gradient of 50% EtOAc hexanes — 100% dicoloromethane. The purest fractions were evaporated of solvent and the resultant residue distilled via a Kugelrohr apparatus (190 °C) to give 26. Ig l-(N-benzimidazole)-4-(o-tolyl)benzene as a clear liquid (48.5% yield).
[0520] Step2: Methylation of l-(N-benzimidazole)-4-( -tolyl)benzene
26. Ig (91.8mmol) of l-(N-benzimidazole)-4-(ø-tolyl)benzene was solubilized with 400mL of toluene in a IL flask equipped with a stir bar. To the stirred solution was carefully added 26. Ig (184mmol) iodomethane and then was allowed to reflux for 2 hours. Next, the condenser was removed and a stream of N2 was passed over the flask to remove excess iodomethane. After the volume of the solution was reduced by half, it was cooled and the white solids collected on a filter and rinsed with toluene followed by hexanes. 35. Og l-(N-[2- methylbenzimidazole])-4-(o-tolyl)benzene was achieved after drying in vacuo (90.0% yield).
[0521] Step 3: Synthesis of fac(wer)-iridium(III) tris(l-(N-[2- methylbenzimidazole])-4-(o-tolyl)benzene
250mL 2-methoxyethanol was purged with N2 and refluxed in a 500mL round bottom flask equipped with a stir bar. After deoxygenation of the solvent, the flask was cooled and 10. Og (23.5mmol) l-(N-[2-methylbenzimidazole])-4-(o-tolyl)benzene was added along with 2.1g (5.86mmol) IrCl3 ' 3H O and 4.1g (17.6mmol) silver(I) oxide. The mixture was refluxed for 30 minutes whereupon an additional 4.1g (17.6mmol) silver(I) oxide was added. After heating for an additional 1.5 hours at reflux, HPLC indicated favorable formation of both the mer and fac isomers (~1 :2 ratio). The reaction mixture was cooled and filtered. Whereas the filtrate was put to the side (mer-rich), the resulting solids were removed the filter, stirred vigorously in 300mL MeCl2 and filtered again. This process was performed a second time and the 600mL of dichloromethane filtrates were evaporated of solvent to give beige solids that were purified on a silica gel column using a gradient of 20% dichloromethane — > 100% dichloromethane to give ~2.5g iridium(III) tris(l-(N-[2-methylbenzimidazole])-4-(o- tolyl)benzene as off-white solids. This material was sublimed in vacuo and afforded 1.5g to be tested in an OLED device (97.8% HPLC assay, 1HNMR confirmed, λmax emission: 466nm, ox: 0.52 (r), 77K excited state lifetime: 67 μsec). The mer-rich filtrate was evaporated of solvent and the residue solubilized in dichloromethane and purified on a column of silica using a gradient of EtoAc/hexanes as eluent. The mer fractions were evaporated of solvent to give ~1.0g mer iridium(III) tris(l-(N-[2-methylbenzimidazole])-4- (o-tolyl)benzene as an off-white solid (98.0% mer) that converted to fac (3:1 mer:fac) upon sublimation (!H NMR confirmed, λmax emission: 468nm, ox: 0.43 (i), 77K excited state lifetime: 48 μsec).
Device fabrication and measurement
[0522] All devices were fabricated by high vacuum (<10" Torr) thermal evaporation.
The anode electrode was ~1200 A of indium tin oxide (ITO). The cathode consisted of 10 A of LiF followed by 1,000 A of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) immediately after fabrication, and a moisture getter was incorporated inside the package. The devices consisted of either one electron transporting layer layer (ETL2) or two ETL layers (ETL2 and ETL1). ETL2 refers to the ETL adjacent to the emissive layer (EML) and ETL1 refers to the ETL adjacent to ETL2.
[0523] Device spectral measurements were done using a PR-705 spectroradiometer manufactured by Photoresearch Inc. Incoming light was focused into the camera and was dispersed by a holographic diffraction grating. The dispersed spectrum was measured by a thermo-electrically cooled silicon diode array detector. The cooled detector was housed in a hermetically sealed, pressurized chamber allowing the instrument to make stable and repeatable measurements. Two on-board microprocessors controlled the hardware and mathematically calculated photometric and colorimetric values for the acquired spectral data during a measurement. The PR-705 measured accurate luminance in the visible spectral range from 380-780 nm.
Example 20
[0524] The organic stack consisted of sequentially, from the ITO surface, 100 A of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of 4,4'-bis(N-carbazolyl)biphenyl (CBP) doped with 6 wt% of Iridium(III) bis[(2-(5'-biphenyl)- 2-pyridinato-N, 2)] ( 1 -phenyl-3 -methyl-imidazolin-2-ylidene-C, C2 ) as the emissive layer (EML), 100 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2, and 400 A of tris(8-hydroxyquinolinato)aluminum (Alq3) as the ETL1.
Comparative Example 1
[0525] The organic stack consisted of sequentially, from the ITO surface, 100 A of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[Ν-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTLl), 300 A of 4,4'-bis(N-carbazolyl)biphenyl (CBP) doped with 4.5 wt% of Ir(5'-Phppy)3 as the emissive layer (EML), 100 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2, and 400 A of tris(8-hydroxyquinolinato)aluminum (Alq ) as the ETL1.
Example 21
[0526] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of 4,4'-bis(N-carbazolyl)biρhenyl (CBP) doped with 12 wt% of Iridium(III) bis[(2-(5'- biphenyl)-2-pyridinato-N,A)] (l-phenyl-3-methyl-imidazolin-2-ylidene-C,A ) as the emissive layer (EML), 100 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4- phenylphenolate (BAlq) as the ETL2, and 400 A of tris(8-hydroxyquinolinato)aluminum (Alq3) as the ETLl.
Example 22
[0527] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of 4,4'-bis(N-carbazolyl)biphenyl (CBP) doped with 6 wt% of mer-iridium(III)tris[l,(2-iodo- 9,9-dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C ] as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2. There is no ETL1.
Comparative Example 2
[0528] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of 4,4'-bis(N-carbazolyl)biphenyl (CBP) doped with 6 wt% of Ir(F2ppy)3 as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2. There is no ETL1.
Example 23
[0529] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of 4,4'-bis(N-carbazolyl)biphenyl (CBP) doped with 12 wt% ofmer-iridium(III)tris[l,(2-iodo- 9'
9,9-dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C ] as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL. There is no ETL1.
Example 24
[0530] The organic stack consists of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of 4,4'-bis(N-carbazolyl)biphenyl (CBP) doped with 6 wt% of mer-iridium(III)tris[l,(2-iodo- 9'
9,9-dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C ] as the emissive layer (EML), 100 A of HPT as the ETL2 and 300 A of aluminum(III)bis(2-methyl-8- hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL1.
Example 25 [0531] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of 4,4'-bis(N-carbazolyl)biphenyl (CBP) doped with 12 wt% of mer-iridium(III)tris[l,(2-iodo- 9,9-dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C2 ] as the emissive layer (EML), 100 A of HPT as the ETL2 and 300 A of aluminum(III)bis(2-methyl-8- hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL1.
Example 26
[0532] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of l,3-bis(N-carbazolyl)benzene (mCP) doped with 6 wt% of mer-iridium(IIι)tris[l,(2-iodo-9,9- dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C2 ] as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2. There is no ETL1.
Comparative Example 3
[0533] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of l,3-bis(N-carbazolyl)benzene (mCP) doped with 6 wt% of Ir(F2ppy)3 as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2. There is no ETL1.
Example 27
[0534] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of l,3-bis(N-carbazolyl)benzene (mCP) doped with 12 wt% of mer-iridium(III)tris[l,(2-iodo- 9,9-dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C2 ] as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2. There is no ETL1. Example 28
[0535] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of l,3-bis(N-carbazolyl)benzene (mCP) doped with 6 wt% of mer-iridium(III)tris[l,(2-iodo-9,9- dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C ] as the emissive layer (EML), 100 A of HPT as the ETL2 and 300 A of aluminum(III)bis(2-methyl-8- hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL1.
Example 29
[0536] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of l,3-bis(N-carbazolyl)benzene (mCP) doped with 12 wt% of mer-iridium(III)tris[l,(2-iodo- 9,9-dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C2 ] as the emissive layer (EML), 100 A of HPT as the ETL2 and 300 A of aluminum(III)bis(2-methyl-8- hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL1.
Example 30
[0537] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of l,3-bis(N-carbazolyl)benzene (mCP) doped with 6 wt% of fac-iridium(III)tris[l,(2-iodo-9,9- dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C2 ] as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2. There is no ETLl.
Example 31
[0538] The organic stack consists of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of l,3-bis(N-carbazolyl)benzene (mCP) doped with 6 wt% of fac-iridium(III)tris[l,(2-iodo-9,9- dimethylfluorenyl)-3-methyl-benzimidazolin-2-ylidene-C,C2 ] as the emissive layer (EML), 100 A of HPT as the ETL2 and 300 A of aluminum(III)bis(2-methyl-8- hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL1.
Example 32
[0539] The organic stack consists of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 50 A of Ir(l-Ph-3-Me-imid)3 as the electron blocking layer (EBL), 300 A of 4,4'-bis(N- carbazolyl)biphenyl (CBP) doped with 4.5 wt% of Ir(5'-Phppy)3 as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2. There is no ETL1.
Example 33
[0540] The organic stack consists of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of Ir(l-Ph-3-Me-imid)3 as the emissive layer (EML), and 400 A of aluminum(III)bis(2-methyl- 8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2. There is no ETL1.
Example 34
[0541] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of l,3-bis(triphenylsilyl)benzene (UGH) doped with 6 wt% of Ir(l-Ph-3-Me-imid)3 as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4- phenylphenolate (BAlq) as the ETL2. There is no ETL1.
Example 35
[0542] The organic stack consists of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 A of l,3-bis(triphenylsilyl)benzene (UGH) doped with 12 wt% of Ir(l-Ph-3-Me-imid) as the emissive layer (EML), 100 A of HPT as the ETL2 and 300 A of aluminum(III)bis(2-methyl- 8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL1. [0543] The external quantum efficiencies and the CIE coordinates of Examples 20-35 and Comparative Examples 1-4 are summarized in Table B.
Table B n . External quantum Example EML Doping EχL2 ETL1 efficiency at 10 CIE mA/cm2 (%)
20
Figure imgf000409_0001
methyl-imidazolin^-ylidene-CA ) CBP: Iridiu (III) bis[(2-(5'-biphenyl)- 0.30, 21 2-pyridinato-N,C2')] (l-phenyl-3- 12 BAlq Alq3 5.35 0.63 methyl-imidazolin-2-ylidene- C,0 ) CBP: mer-iridium(III)tris[l,(2-iodo- 0.17, 22 9,9-dimethylfluorenyl)-3-methyl- BAlq none 0.4 0.33 benzimidazolin-2-ylidene-C,C2 ] CBP: mer-iridium(III)tris[l,(2-iodo- 0.18, 23 9,9-dimethylfluorenyl)-3-methyl- 12 BAlq none 0.5 0.37 benzimidazolin-2-ylidene-C,C2 ] CBP : mer-iridium(III)tris[ 1 ,(2-iodo- 0.18, 24 9,9-dimethylfluorenyl)-3-methyl- HPT BAlq 0.3 0.32 benzimidazolin-2-ylidene-C,C2 ] CBP: mer-iridium(III)tris[l,(2-iodo- 0.18, 25 9,9-dimethylfluorenyl)-3-methyl- 12 HPT BAlq 0.4 0.37 benzimidazolin-2-ylidene-C,C2 ] mCP: mer-iridium(III)tris[l,(2-iodo- 0.17, 26 9,9-dimethylfluorenyl)-3-methyl- BAlq none 2.2 0.37 benzimidazolin-2-ylidene-C,C2 ] mCP: mer-iridium(III)tris[l,(2-iodo- 0.17, 27 9,9-dimethylfluorenyl)-3-methyl- 12 BAlq none 1.3 0.36 benzimidazolin-2-ylidene-C,C2 ] mCP: mer-iridium(III)tris[l ,(2-iodo- 0.18, 28 9,9-dimethylfluorenyl)-3-methyl- HPT BAlq 2.1 0.40 benzimidazolin-2-ylidene-C,C2 ] mCP: mer-iridium(III)tris[l,(2-iodo- 0.18, 29 9,9-dimethylfluorenyl)-3-methyl- 12 HPT BAlq 2.5 0.40 benzimidazolin-2-ylidene-C,C2 ] mCP: fac-iridium(III)tris[l,(2-iodo- 0.17, 30 9,9-dimethylfluorenyl)-3-methyl- BAlq none 1.4 0.33 benzimidazolin-2-ylidene-C,C2 ] mCP: fac-iridium(III)tris[l ,(2-iodo- 0.17, 31 9,9-dimethylfluorenyl)-3-methyl- HPT BAlq 1.4 0.36 benzimidazolin-2-ylidene-C,C2 ] 32 CBP:Ir(5'-Phppy)3 0.30, 4.5 BAlq Alq3 11.8 0.65 neat 0.19, 33 Ir(l-Ph-3-Me-imid)3 BAlq none 0.6 layer 0.36 34 UGH: Ir(l-Ph-3-Me-imid)3 0.17, 12 BAlq none 1.3 0.20 0.17, 35 UGH: Ir(l-Ph-3-Me-imid)3 12 HPT BAlq 1 0.18
Comparative 0.31, CBP:Ir(5'-Phppy)3 4.5 BAlq Alq3 7.1 example 1 0.64
Comparative 0.17, CBP:Ir(F2ppy)3 6 BAlq none 0.5 example 2 0.30
Comparative 0.16, mCP:Ir(F2ρpy)3 6 BAlq none 4 example 3 0.36
Comparative Neat 0.15, UGH BA1Q None 0.4 example 4 layer 0.12
[0544] Figure 27 shows the external quantum efficiency vs. current density of examples 20-21 and comparative example 1. Figure 28 shows the electroluminescence spectra of examples 20-21 and comparative example 1 at 10 mA/cm2. It can be seen that the device efficiency and emission color are similar for Iridium(III) bis[(2-(5'-biphenyl)-2- pyridinato-NC2)] ( 1 -phenyl-3 -methyl-imidazolin-2-ylidene-C, C2 ) and Ir(5'-Phppy)3. Figure 29 shows the operational stability of example 20 vs. comparative example 1. The halflife, Ti/2, defined as the time required for the electroluminescence to drop to 50% of its initial value, is ~200 hrs for comparative example 1. This is slightly longer than that of example 10 (-120 hrs).
[0545] Figure 30 shows the external quantum efficiency vs. current density of examples 22-25. Figure 31 shows the electroluminescence spectra of examples 22-25. It can be seen these devices with CBP as the host emit light blue color with 0.3 to 0.7% external quantum efficiency.
[0546] Figure 32 shows the external quantum efficiency vs. current density of examples 26-29. Figure 33 shows the electroluminescence spectra of examples 26-29. It can be seen that these devices with mCP as the host emit light blue color with 1.4 to 3.4% external quantum efficiency which are higher than examples 22-25 which have the exact device structure except that example 22-25 use CBP as the host. [0547] Figure 34 shows the external quantum efficiency vs. current density of examples 30 and 31. Figure 35 shows the electroluminescence spectra of examples 30 and 31. Examples 30 and 31 devices are analogous to examples 26 and 28 respectively. The difference is that examples 30 and 31 utilize the facial isomer of the invention compound, whereas examples 26 and 28 utilize the meridional isomer of the invention compound. They all utilize mCP as the host. It can been seen that devices with the meridional isomer are more efficient than devices with the facial isomer (see Table B) in this device structure. [0548] Figure 36 shows the external quantum efficiency vs. current density of example 32. Figure 37 shows the electroluminescence spectra of example 32. It can be seen the device with Ir(l-Ph-3-Me-imid) as the electron blocking layer has a device efficiency of 11.8% at 10 mA/cm2, significantly enhanced from 7.1% at 10 mA/cm2 obtained from comparative example 1 which does not utilize an electron blocking layer. [0549] Figure 38 shows the external quantum efficiency vs. current density of example 33. Figure 39 shows the electroluminescence spectra of example 33. It can be seen the device does not emit through Ir(l-Ph-3-Me-imid) but rather through BAlq, which is the layer next to the Ir(l-Ph-3-Me-imid)3 layer. It suggests hole transport is the dominant role of the Ir(l-Ph-3-Me-imid)3 layer in this device structure.
[0550] Figure 40 shows the external quantum efficiency vs. current density of example 34 and 35. Figure 41 shows the electroluminescence spectra of example 34 and 35. The device structures of examples 34 and 35 include the compound Ir(l-Ph-3-Me-imid)3 doped into the high energy host, UGH. The devices have different ETL layers. Example 34 has only a BA1Q ETL, and example 35 has a 100 A layer of hole blocking HPT followed by BA1Q. HPT is believed to be an effective hole blocking material. In these devices, high energy emission is observed with peak intensities at 384 nm and 404 nm. Additional peaks are observed at 429 nm, 451 nm, and 503 nm. A comparison of the PL spectra of the dopant (Figure 18) and the EL spectra (Figure 41), suggests that the high energy peaks are believed to be attributable to emission from the dopant.
[0551] Figure 43 shows the quantum efficiency vs. current density for comparative example 4. Figure 44 shows the normalized electroluminescence spectra for Comparative example 4, which has a similar device structure to example 34 using the UGH host except the host is not doped. It can be seen that the device of comparative example 4 emits almost entirely from the NPD HTL layer and has an EL peak intensity at 440nm. It is believed that the emission from the NPD is due to the fact that UGH acts as a poor hole conductor. Therefore, all recombination may take place at the NPD/UGH interface. It can be seen from Figure 41 that the device having an undoped UGH host in comparative example 4 has no high energy peaks below 440 nm, as was observed in the devices with the doped UGH hosts of examples 34 and 35. [0552] Figure 42 shows the subtracted EL spectra of example 34 from example 35. This is also shown as the shaded region between the EL spectra of examples 34 and 35. It can be seen that the difference between the devices appears to be an additional contribution from the emission of BAIQ emission in example 34. BAIQ emits with a Gaussian shape and has a peak intensity at 480 nm, which looks very similar to the spectral difference. BAIQ may emit in the device of example 34 because Ir(l-Ph-3-Me-imid)3 may act as a good hole conductor allowing for recombination to take place in the BAIQ layer near the interface with the emissive layer. The addition of the HPT hole blocking material may prevent hole electron recombination from taking place in BAIQ resulting in the spectral difference between examples 34 and 35. [0553] The addition of another layer between NPD and the emissive layer may be desirable to increase the emission from the dopant. It has been shown in R J. Holmes et al. APL 2003, 83, 3818), which is incorporated by reference in its entirety, that a layer of mCP inserted between NPD and the emissive layer may be necessary to reduce NPD emission and improve efficiency. Holmes describes a device using a blue emitting dopant in a high energy aryl-silane host which is a structural isomer of the UGH host used in examples 34 and 35. It is believed that similar device modifications for UGH: Ir(l-Ph-3-Me-imid) would have a comparable effect. Thus the insertion of different materials between NPD and the UGH: Ir(l-Ph-3-Me-imid)3 emissive layer may improve the intensity and spectral contribution from the UV emitting dopant. [0554] Table C below indicates the dopants used for the devices of Examples 36-55.
Table C
Figure imgf000412_0001
Figure imgf000413_0001
412
Figure imgf000414_0001
Example 36 [0555] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-ρhenylamino]biρhenyl (α-NPD), as the hole transporting layer (HTL), 300 A of UGH5 doped with 6 wt% Dopant A as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
Example 37
[0556] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of
UGH5 doped with 6 wt% Dopant B as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
[0557] Fig. 45 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/UGH5: Dopant A (6%, 300)/BAlQ(400) and device
CuPc(100)/NPD(300)/UGH5: Dopant B (6%, 300)/BAlQ(400).
[0558] Fig. 46 shows plots of quantum efficiency vs. current density for device
CuPc(100)/NPD(300)/UGH5: Dopant A (6%, 300)/BAlQ(400) and device
CuPc(100)/NPD(300)/UGH5: Dopant B (6%, 300)/BAlQ(400).
[0559] Fig. 47 shows plots of the electroluminescent spectra of device
CuPc(100)/NPD(300)/UGH5: Dopant A (6%, 300)/BAlQ(400) and device
CuPc(100)/NPD(300)/UGH5: Dopant B (6%, 300)/BAlQ(400).
Example 38
[0560] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of mCBP doped with 6 wt% Dopant C as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
Example 39
[0561] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of mCBP doped with 6 wt% Dopant D as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
[0562] Fig. 48 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/mCBP: Dopant C (6%, 300)/BAlQ(400) and device
CuPc(100)/NPD(300)/mCBP:Dopant D (6%, 300)/BAlQ(400).
[0563] Fig. 49 shows plots of quantum efficiency vs. current density for device
CuPc(100)/NPD(300)/mCBP: Dopant C (6%, 300)/BAlQ(400) and device
CuPc(100)/NPD(300)/mCBP: Dopant D (6%, 300)/BAlQ(400).
[0564] Fig. 50 shows plots of the electroluminescent spectra of device
CuPc(100)/NPD(300)/mCBP: Dopant C (6%, 300)/BAlQ(400) and device
CuPc(100)/NPD(300)/mCBP: Dopant D (6%, 300)/BAlQ(400).
[0565] Fig. 66 shows plots of the plot of operation lifetime of device
CuPc(100)/NPD(300)/UGH5: Dopant D (6%, 300)/BAlQ(400).
Example 40
[0566] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of mCBP doped with 6 wt% Dopant E as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
Example 41
[0567] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of mCBP doped with 6 wt% Dopant F as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydiOxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
[0568] Fig. 51 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/mCBP: Dopant E (300, 6%)/BAlQ(400) and device
CuPc(100)/NPD(300)/mCBP: Dopant F (300, 6%)/BAlQ(400).
[0569] Fig. 52 shows plots of quantum efficiency vs. current density for device
CuPc(100)/NPD(300)/mCBP: Dopant E (300, 6%)/BAlQ(400) and device CuPc(100)/NPD(300)/mCBP: Dopant F (300, 6%)/BAlQ(400). [0570] Fig. 53 shows plots of the electroluminescent spectra of device
CuPc(100)/NPD(300)/mCBP: Dopant E (300, 6%)/BAlQ(400) and device CuPc(100)/NPD(300)/mCBP: Dopant F (300, 6%)/BAlQ(400).
Example 42
[0571] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of UGH5 doped with 6 wt% Dopant G as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
[0572] Fig. 54 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/UGH5: Dopant G (6%, 300)/BAlQ(400). [0573] Fig. 55 shows plots of quantum efficiency vs. current density for
CuPc(100)/NPD(300)/UGH5: Dopant G (6%, 300)/BAlQ(400). [0574] Fig. 56 shows plots of the electroluminescent spectra of
CuPc(100)/NPD(300)/UGH5: Dopant G (6%, 300)/BAlQ(400).
Example 43
[0575] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of mCP doped with 6 wt% Dopant H as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
Example 44
[0576] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of CBP doped with 6 wt% Dopant I as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL). Example 45
[0577] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of mCBP doped with 6 wt% Dopant J as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
[0578] Fig. 57 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/mCP: Dopant H (6%, 300)/BAlQ(400), device CuPc(100)/NPD(300)/CBP: Dopant I (6%, 300)/BAlQ(400), and device CuPc(100)/NPD(300)/mCBP: Dopant J (6%, 300)/BAlQ(400).
[0579] . Fig. 58 shows plots of quantum efficiency vs. current density for device
CuPc(100)/NPD(300)/mCP: Dopant H (6%, 300)/BAlQ(400), device CuPc(100)/NPD(300)/CBP: Dopant I (6%, 300)/BAlQ(400), and device CuPc(100)/NPD(300)/mCBP: Dopant J (6%, 300)/BAlQ(400). [0580] Fig. 59 shows plots of the electroluminescent spectra of device
CuPc(100)/NPD(300)/mCP: Dopant H (6%, 300)/BAlQ(400), device CuPc(100)/NPD(300)/CBP: Dopant I (6%, 300)/BAlQ(400), and device CuPc(100)/NPD(300)/mCBP: Dopant J (6%, 300)/BAlQ(400).
Example 46
[0581] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of mCBP doped with 6 wt%> Dopant K as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
Example 47
[0582] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of mCBP doped with 6 wt% Dopant L as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
Example 48
[0583] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of UGH5 doped with 6 wt% Dopant M as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
[0584] Fig. 60 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/mCBP: Dopant K (6%, 300)/BAlQ(400), device CuPc(100)/NPD(300)/mCBP: Dopant L (6%, 300)/BAlQ(400), and device CuPc(100)/NPD(300)/UGH5: Dopant M (6%, 300)/BAlQ(400). [0585] Fig. 61 shows plots of quantum efficiency vs. current density for device
CuPc(100)/NPD(300)/mCBP: Dopant K (6%, 300)/BAlQ(400), device CuPc(100)/NPD(300)/mCBP: Dopant L (6%, 300)/BAlQ(400), and device CuPc(100)/NPD(300)/UGH5: Dopant M (6%, 300)/BAlQ(400). [0586] Fig. 62 shows plots of the electroluminescent spectra of device
CuPc(100)/NPD(300)/mCBP: Dopant K (6%, 300)/BAlQ(400), device CuPc(100)/NPD(300)/mCBP: Dopant L (6%, 300)/BAlQ(400), and device CuPc(100)/NPD(300)/UGH5: Dopant M (6%, 300)/BAlQ(400).
Example 49
[0587] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of UGH5 doped with 6 wt% Dopant N as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
Example 50
[0588] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of UGH5 doped with 6 wt% Dopant O as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylρhenolate (BAlq) as the electron transporting layer (ETL).
Example 51
[0589] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of UGH5 doped with 6 wt% Dopant P as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the electron transporting layer (ETL).
[0590] Fig. 63 shows plots of current vs. voltage for device
CuPc(100)/NPD(300)/UGH5: Dopant N (6%, 300)/BAlQ(400), device CuPc(100)/NPD(300)/UGH5: Dopant O (6%, 300)/BAlQ(400), and device CuPc(100)/NPD(300)/UGH5: Dopant P (6%, 300)/BAlQ(400). [0591] Fig. 64 shows plots of quantum efficiency vs. current density for device
CuPc(100)/NPD(300)/UGH5: Dopant N (6%, 300)/BAlQ(400), device CuPc(100)/NPD(300)/UGH5: Dopant O (6%, 300)/BAlQ(400), and device CuPc(100)/NPD(300)/UGH5: Dopant P (6%, 300)/BAlQ(400). [0592] Fig. 65 shows plots of the electroluminescent spectra of device
CuPc(100)/NPD(300)/UGH5: Dopant N (6%, 300)/BAlQ(400), device CuPc(100)/NPD(300)/UGH5: Dopant O (6%, 300)/BAlQ(400), and device CuPc(100)/NPD(300)/UGH5: Dopant P (6%, 300)/BAlQ(400).
Example 52
[0593] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naρhthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of l,3-N,N-dicarbazole-benzene (mCP) doped with 6 wt% Dopant Q as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2. There was no ETL1.
Example 53 [0594] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of l,3-N,N-dicarbazole-benzene (mCP) doped with 6 wt% of Dopant Q as the emissive layer (EML), and 100 A of 2,3, 6,7, 10,11 -hexaphenyltriphenylene (HPT) as the ETL2, and 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL1. [0595] Fig. 67 shows plots of current vs. voltage of device CuPc(l 00 A)/NPD(300
A)/mCP:Dopant Q(300 A,6%)/BA1Q(400 A) and device CuPcQOO A)/NPD(300 A)/mCP:Dopant Q(300 A,6%)/HPT(100 A)/BA1Q(400 A).
[0596] Fig. 68 shows plots of quantum efficiency vs. current density for device
CuPc(100 A)/NPD(300 A)/mCP: Dopant Q(300 A,6%)/BA1Q(400 A) and device CuPc(100 A)/NPD(300 A)/mCP:Dopant Q(300 A,6%)/HPT(100 A)/BA1Q(400 A). [0597] Fig. 69 shows the electroluminescent specfra for device CuPc(100
A)/NPD(300 A)/mCP: Dopant Q (300 A,6%)/BA1Q(400 A) and device CuPc(100 A)/NPD(300 A)/mCP:Dopant Q(300 A,6%)/HPT(100 A)/BA1Q(400 A). [0598] Fig. 73 shows plots of operational lifetime of device CuPc(l 00 A)/NPD(300
A)/mCP: Dopant Q (300 A,6%)/BA1Q(400 A) and device CuPc(100 A)/NPD(300 A)/mCP:Dopant Q(300 A,6%)/HPT(100 A)/BA1Q(400 A) measured at 5 mA/cm2.
Example 54
[0599] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of l,3-bis(triphenylsilyl)benzene (UGH5) doped with 12 wt% Dopant Q as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2. There was no ETL1.
Example 55
[0600] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 100 A of 4,4',4"-Tris(carbazol-9-yl)-triphenylamine (TCTA), as the other hole transporting layer HTL2, 300 A of l,3-bis(triρhenylsilyl)benzene (UGH5) doped with 12 wt% Dopant Q as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4- phenylphenolate (BAlq) as the ETL2. There was no ETL1.
[0601] Fig. 70 shows plots of current vs. voltage of device CuPc(100 A)/NPD(300
A)/ UGH5:Dopant Q(300 A,12%)/BA1Q(400 A) and device CuPc(100 A)/NPD(300 A)/
TCTA(100 A)/UGH5:Dopant Q(300 A,12%)/BA1Q(400 A).
[0602] Fig. 71 shows plots of quantum efficiency vs. current density for device
CuPc(100 A)/NPD(300 A)/ UGH5:Dopant Q(300 A,12%)/BA1Q(400 A) and device
CuPc(100 A)/NPD(300 A)/ TCTA(100 A)/UGH5:Dopant Q(300 A,12%)/BA1Q(400 A).
[0603] Fig. 72 shows the electroluminescent spectra for device CuPc(100
A)/NPD(300 A)/ UGH5:Dopant Q(300 A,12%)/BA1Q(400 A) and device CuPc(100
A)/NPD(300 A)/ TCTA(100 A)/UGH5:Dopant Q(300,12%)/BA1Q(400 A).
Example 56
[0604] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of Ir(bmi)3 doped with 6 wt% of Ir(4,6-F2ppy) as the emissive layer (EML), 400 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL2. There was no ETL1.
Example 57
[0605] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'-bis[N-(l- naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of
Ir(bmi) doped with 6 wt% of Ir(F2ppy) as the emissive layer (EML), and 100 A of
2,3,6,7,10,11-hexaphenyltriphenylene (HPT) as the ETL2, and 400 A of aluminum(III)bis(2- methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq) as the ETL1.
[0606] Figure 74 shows plots of the current density vs. voltage for device Examples
56 and 57. Figure 75 shows plots of the quantum efficiency vs. current density for device
Examples 56 and 57. Figure 76 shows plots of the electroluminescent spectra for device
Examples 56 and 57.
Example 58
[0607] The organic stack consisted of sequentially, from the ITO surface, 100 A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'- bis[N-(l-naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of Ir(bmi) doped with 6 wt% of Ir(5-ρhppy) as the emissive layer (EML), and 100 A of aluminum(III)bis(2-methyl-8-hydroxyquinolinato)4-phenylphenolate (BAlq), and 400 A of tris(8-hydroxyquinolinato)aluminum (Alq3) as the ETL1.
Example 59
[0608] The organic stack consisted of sequentially, from the ITO surface, 100
A thick of copper phthalocyanine (CuPc) as the hole injection layer (HIL), 300 A of 4,4'- bis[N-(l-naphthyl)-N-phenylamino]biphenyl (α-NPD), as the hole transporting layer (HTL), 300 A of Ir(bmi) doped with 6 wt% of Ir(5-phppy) as the emissive layer (EML), and 100 A of 2,3,6,7,10,11-hexaphenyltriphenylene (HPT) as the ETL2, and 400 A of tris(8- hydroxyquinolinato)aluminum (Alq3) as the ETL1.
[0609] Figure 77 shows plots of current density vs. voltage for device Examples 58 and 59. Figure 78 shows plots of the quantum efficiency vs. current density for device Examples 58 and 59. Figure 79 shows plots of the electroluminescent spectra for device Examples 58 and 59. Figure 80 shows plots of operation lifetime of device Examples 56, 58, and 59.
Synthesis of carbene dopants
Example 60, 61: Synthesis of fac-iridium(III) tris (l-(2-naphthyl-3-methyl- benzimidazoline^-ylidene-CjC2) and mer-iridium(III) tris (l-(2-naphthyl-3-methyl- benzimidazoline^-ylidene-CjC2) [Dopant C, D]
[0610] A 3 L round-bottomed flask was charged with 113.83g of silver(I) oxide, 38g of 1 -(2 -naphthyl)-3-methyl-benzimidazolate iodide, 9.1 g of iridium trichloride hydrate, and 2000 mL of 2-ethoxyethanol. The reaction was stirred and heated at 120oC for 2 h under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure(20mmHg). Filtration through Celite using dichloromethane as the eluent was performed to remove the silver(I) salts. A light brown solution was obtained and further purified by flash column chromatography on silica gel using dichloromethane as the eluent and 6g (25.2%) of iridium complex was obtained. The mer isomer was selectively crystallized from a mixture of dichloromethane and methanol. The mother liquid was evaporated to dryness and the residue was recrystallized from dichloromethane to obtain the fac isomer.
Example 62: Synthesis of f ac-iridium(III) tris (l-(4,5-dimethylphenyl)-3-methyl- benzimidazoline-2-ylidene- C2) [Dopant A]
[0611] A 3 L round-bottomed flask was charged with 66.1 Ag of silver(I) oxide, 21g of l-(4,5-dimethylphenyl)-3-methyl-benzimidazolate iodide, 5.33 g of iridium trichloride hydrate, molecular sieve (200g) and 1108 mL of 2-ethoxyethanol. The reaction was stirred and heated at 120°C for 3.5 h under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure(20mmHg). Filtration through Celite using dichloromethane as the eluent was performed to remove the silver(I) salts. A light brown solution was obtained and further purified by flash column chromatography on silica gel using dichlormethane as the eluent and 9g (60%) of iridium complex was obtained. The fac isomer was selectively crystallized from a mixture of dichloromethane and methanol.
Example 63: Synthesis of f ac-iridium(III) tris (l-(4,5-dimethylphenyι)-3-methyl-5,6- dimethyl-benzimidazoline^-ylidene-C 2) [Dopant B]
[0612] A 3 L round-bottomed flask was charged with 118.14g of silver(I) oxide, 40g of l-(4,5-dimethylphenyl)-3-methyl-benzimidazolate iodide, 9.44g of iridium trichloride hydrate, molecular sieve (lOOg) and 2000 mL of 2-ethoxyethanol. The reaction was stirred and heated at 120°C for 3h under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure(20mmHg). Filtration through Celite using dichloromethane as the eluent was performed to remove the silver(I) salts. A light brown solution was obtained and further purified by flash column chromatography on silica gel using dichloromethane as the eluent and 9g (35%) of iridium complex was obtained. The fac isomer was selectively crystallized from a mixture of dichloromethane and methanol.
Example 64: Synthesis of fac-iridium(III) tris (l-(4-chlorolphenyl)-3-(4-chlorophenyl) - imidazoline-2-ylidene-C, C2)
[0613] A 100ml round-bottomed flask was charged with 177.9 mg of silver(I) oxide,
250mg of l,3-bis(4-chlorophenyl)imidazolium Chloride, 71.09 mg of iridium trichloride hydrate, and 20 mL of 2-ethoxyethanol. The reaction was stirred and heated at 120°C for lh under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced ρressure(20mmHg). Filtration through Celite using dichloromethane as the eluent was performed to remove the silver(I) salts. A light brown solution was obtained and further purified by flash column chromatography on silica gel using dichloromethane as the eluent and 50mg (25%) of iridium complex was obtained. The fac isomer was selectively crystallized from a mixture of dichloromethane and methanol.
Example 65: Synthesis of Dopant Q
Figure imgf000425_0001
Dopant Q
[0614] A 100 mL round-bottomed flask was charged with 827 mg of ligand Q, 500 mg of benzylpyridine dichloro bridge dimer, 470 mg of sodium carbonate and 100 mL of 2- ethoxyethanol. The reaction was stirred and heated at 135°C for 3h under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure(20mmHg). A light brown solution was obtained and further purified by flash column chromatography on silica gel using dichlormethane as the eluent. 510 mg (78%) of iridium complex was obtained.
Synthesis of Osmium Carbene Complexes
Example 66: Synthesis of Osmium Carbene Complex 1 (Osl) [0615] Step l: Synthesis of Os 1-A
Figure imgf000425_0002
Os l-A
A three neck 1000 mL round bottom flask was charged with 19.1 g of benzimidazole, 25.0 g of 1,3-diiodobenzene, 1.46 g of copper (I) iodide, 44.7 g of potassium carbonate, 2.77 g of 1,10-phenathroline, and 500 mL of anhydrous N,N-dimethylformamide. The reaction mixture was heated to reflux under nitrogen for 2 days. After cooling to room temperature the reaction was filtered and the solvent removed from the filtrate by rotary evaporation. The crude product was purified by silica gel column chromatography using 95% dichloromethane/methanol as the eluent. The fractions containing the desired material were combined and the solvent removed by rotary evaporation. The product was crystallized from a dichloromethane/ethyl acetate mixture. The product (18 g) was collected by vacuum filtration as a white solid. [0616] Step 2: Synthesis of Osl-B
Figure imgf000426_0001
Os l-B
A 1000 mL round bottom flask was charged with 15 g of Compound A, 30 g of iodomethane, and 400 mL of N,N-dimethylformamide. The mixture was heated to approximately 60°C for 18 hours. The mixture was filtered and the solids were washed with ethyl acetate. The solids were then slurried in 400 ml of refluxing methanol, cooled, and then filtered to yield 20 g of the desired product as a white solid. [0617] Step 3: OsH4(PPh3)3-
A 1000 mL three neck round bottom flask was charged with 3.6 g of triphenylphosphine and 100 ml of ethanol. The mixture is heated to reflux and 1.0 g of ammonium hexachloroosmiate was added. A solution of 0.43 g of sodium borohydride in 50 ml of ethanol is then added dropwise. The reaction is refluxed for 30 minutes and then cooled to room temperature. The off white solids are collected by vacuum filtration. The solids were washed successively with ethanol, water, ethanol, and hexane. [0618] Step 4: Os 1
Figure imgf000426_0002
Os l
[0619] A 250 ml three neck round bottom flask was charged with 4.0 g of compound
B, 3.3 g of OsH4(PPh )3, and 125 mL of N,N-dimethylformamide. The mixture was heated to reflux for 20 hours under nitrogen. The solvent was removed by rotary evaporation and the crude product was purified by silica gel column chromatography using 80% hexanes/ethyl acetate as the eluent. The fractions containing the desired product were combined and the solvent removed by rotary evaporation. The product was crystallized from an ethyl acetate/hexane mixture. The product was confirmed by mass spectroscopy and 1H NMR. [0620] The emission spectra for Os 1 as a solution in toluene (degassed) at room temperature is shown in Figure 81.
Example 67: Synthesis of Osmium Carbene Complex 2 (Os 2) [0621] Step l: Synthesis of Os 2-A
Figure imgf000427_0001
Os 2-A
[0622] To a Solution of CuBr2 (26.8g, 120mmole) in anhydrous Acetontrile
(500ml) at 0°C was added t-butyl nitrite (21.1ml, lόOmmole) dropwise, and then 3-amino-5- bromobenzotrifluori.de (25g, 104.1mmole) was added dropwise. The mixture was stirred at 0°C for 1.5h, then at room temperature for 16 h. The mixture was then concentrated to half of its original volume in vacuo, and then poured into 1 N HCl (620ml). This mixture was extracted with ether (400ml). The organic layer was washed with IN HCl, dried ( Na SO4), filtered, concentrated in vacuo. The residue was purified by flash column chromatography on silica gel using hexanes as the eluent and 18.33g of Os 2-A was obtained. (57.8%) [0623] Step 2: Synthesis of Os 2-B
Figure imgf000427_0002
Os 2-B
A lOOOmL round bottom flask was charged with 13.33 g of compound Os 2-A, 12.43g of benzimidazole, 1.668g of copper (I) iodide, 3.15g of 1,10-phenanthroline, 59.93g of cesium carbonate, and 500ml of N, N-dimethylformamide. The reaction mixture was heated to 150 °C under nitrogen for 60 hours. After cooling to room temperature; the reaction was filtered and the solvent was removed from the filtrate by rotary evaporation. The crude product was purified by silica gel column chromatography using 95% dichloromethane/ethyl acetate mixture. The product Os2-B (lOg, 60%) was collected by vacuum filtration as a white solid. [0624] Step 3: Os2-C
Figure imgf000428_0001
OS2-C
A 1000ml round bottom flask was charged with 8g of compound Os2-C, 60g of iodomethane and 500ml of N,N-dimethylformamide. The mixture was heated to 41 °C for 70hrs. 200ml of toluene was added to induce the precipitation. The mixture was filtered and the solids were washed with ether to yield 9g of Os2-C (64%).
[0625] Step 4: Os 2
Figure imgf000428_0002
A 50ml round bottom flask was charged with 310mg of compound OS2-C, 230mg of OsH4(PPh3)3 and 35 ml of N,N-dimethylformamide. The mixture was heated to 150 °C for 3hrs under nitrogen. The reaction mixture was dumped into water (150ml) and extracted by ether. The ether was removed by rotary evaporation. The residue was purified by column chromatography (SiO2, 80% hexanes/ethyl acetate) to yield Os2. [0626] The emission spectra for Os2 as a solution in toluene (degassed) at room temperature is shown in Figure 82.
Synthesis of Platinum Complexes
Example 68: Synthesis of Ptl52
Figure imgf000429_0001
Pt152
[0627] Ste l: Synthesis of l-[3-(lH-benzimidazole-lyl-methyl)benzyl]-lH- benzimidazole:
To a IL round bottom flask equipped with a stirbar was added 26.8 g benzimidazole (227 mmol) and 12.7 g (227 mmol) finely pulverized potassium hydroxide. These were stirred in 500 mL acetone for 20 minutes at reflux. 20.0 g (78.5 mmol) α,α'-dibromo-m-xylene was then added, and the solution was stirred at reflux for 6 hours followed by room temperature stirring for 72 hours. The cloudy solution was filtered, and the white solids rinsed with acetone. The resulting filtrate was dried on silica and partitioned on a silica gel column using a gradient of 100% acetonitrile - 90% acetronitrile/10% MeOH as eluent. The product fractions were evaporated of solvent to give 5g l-[3-(lH-benzimidazole-lyl-methyl)benzyl]- lH-benzimidazole as a white solid.
Figure imgf000429_0002
[0628] Step 2: Synthesis of l-bromo-α,α'-dibromo-m-xylene
To a IL flask charged with 300 mL carbon tetrachloride was added 50.0 g (270 mmol) 1- bromo-2,6-diemthylbenzene and 100.9 g (567 mmol) N-bromosuccinimide. As this solution was stirred, 200 mg benzoyl peroxide was added, and the mixture was allowed to reflux for 30 minutes. Afterwards, the mixture was cooled, and an additional 200 mg benzoyl peroxide was added and then reheated to reflux for an additional 30 minutes. This process was repeated two more times, and then the mixture was allowed to reflux for 20 hours. Finally, the solution was allowed to cool and then was filtered. Evaporation of the filtrate gave a waxy brown solid that was recrystallized from cyclohexane, filtered, rinsed with hexanes, and dried to give -20 g l-bromo-2,6-dibromo-m-xylene as a white powder. benzoyl peroxide carbon tetrachloride
Figure imgf000430_0002
Figure imgf000430_0001
[0629] Step 3: Synthesis of Benzimidazoliophane-Br
In a 250 mL flask, 2.0 g (5.91 mmol) l-[3-(lH-benzimidazole-lyl-methyl)benzyl]-lH- benzimidazole was solubilized in 100 mL acetone with stirring action. 2.03 g (5.91 mmol) 1- bromo-α,α'-dibromo-m-xylene dissolved in 60 mL acetone was then added dropwise. After addition, the mixture refluxed for 20 hours whereupon white solids developed. The mixture was then cooled, filtered, and the benzmidazoliophane-Br rinsed with acetone to give 3.3 g as a white solid.
Figure imgf000430_0003
[0630] Step 4: Synthesis of Pt (II) benzimidazoliophane (Ptl52)
In a 250 mL three neck flask, 100 mL 2-methoxyethanol was thoroughly degassed (2 hours) with N2 and heat. The solvent was then cooled to 70°C whereupon 1.83 g (1.47 mmol) tetrakistriphenylphosphine platinum (0), 1.00 g (4.02 mmol) benzimidazoliophane-Br and 0.81 g (5.87 mmol) potassium carbonate were added. The mixture was set to reflux for 30 minutes and then immediately cooled. The solution was filtered warm to remove unsolubilized base. Finally, the filtrate was evaporated to 15 mL and enriched with 200 mL methanol to precipitate the product. Filtration of this solution gave yellow solids that were dissolved in methylene chloride and purified on a thin silica gel column using methylene chloride as eluent. Removal of solvent and recrystallization from methylene chloride/methanol gave -0.15 g Pt (II) benzimidazoliophane as a yellow solid as confirmed by NMR (λmax = 535nm (DMF), Ox: 0.72(f) vs. ferrocene, Red: not detectable). KaCOg 2-methoxyethanoI
Figure imgf000431_0001
Figure imgf000431_0002
Pt152
Example 69: Synthesis of Ptl51
Figure imgf000431_0003
[0631] Step 1 : Synthesis of l-[3-(lH-imidazole-lyl-methyl)benzyl]-lH-imidazole
To a 500 mL round bottom flask equipped with a stirbar was added 11.6 g imidazoie (170 mmol) and 9.55 g (170 mmol) finely pulverized potassium hydroxide. These were stirred in 200 mL acetone until the solution became yellow translucent. 15.0 g (56.8 mmol) α,α'-dibromo-m-xylene was then added, and the solution was stirred at room temperature overnight. The cloudy solution was filtered, and the white solids rinsed with acetone. The resulting filtrate was dried on silica and partitioned on a silica gel column using 30/70 acetonitrile/methanol as eluent. The product fractions were evaporated of solvent and the resulting oil recrystallized from ethyl acetate/hexanes to give 8.65 g l-[3-(lH-imidazole-lyl- methyl)benzyl]-lH-imidazole as a white solid.
Figure imgf000431_0004
[0632] Step 2: Synthesis of l-bromo-α,α'-dibromo-m-xylene
To a IL flask charged with 150 mL chlorobenzene was added 24.7 g (134 mmol)l-bromo- 2,6-diemthylbenzene and 48.3g (271 mmol) N-bromosuccinimide. As this solution was stirred, 1.12 g benzoyl peroxide (4.6 mmol) was added and the mixture was allowed to reflux 1 hour (Caution: as the reaction mixture began to heat, a violent exotherm occurred whereby the reaction contents shot up the condenser. It is possible that the mixture could evolve from the condenser for any given reaction). An additional 0.75 g benzoyl peroxide was then added, and the mixture was refluxed for an additional 4 hours. Finally, the solution was allowed to cool to room temperature and stirred overnight. This solution was filtered, and the solids rinsed with chlorobenzene. Evaporation of the solvent gave a waxy brown solid that was distilled twice via Kugelrohr to remove impurities. The solids were then recrystallized from methanol to give ~15g l-bromo-2,6-dibromo-m-xylene as a white powder.
Figure imgf000432_0001
[0633] Step 3 : Synthesis of Imidazoliophane-Br
In a IL flask, 8.31 g (34.9 mmol) l-[3-(lH-imidazole-lyl-methyl)benzyl]-lH-imidazole was solubilized in 400 mL acetone with stirring action. 12.0 g (34.9 mmol) l-bromo-α,α'- dibromo-m-xylene dissolved in 150 mL acetone was then added dropwise. After addition, the mixture refluxed for 2 hours whereupon white solids developed. The mixture was then cooled, filtered, and the Imidazoliophane-Br rinsed with acetone. This product was then recrystallized from methanol to give 4.0 g as a white powder. The remaining portion (+10 g) was left as a crude light brown solid.
acetone
Figure imgf000432_0002
Figure imgf000432_0003
[0634] Step 4: Synthesis of Pt (II) imidazoliophane
In a IL three neck flask, 200 mL 2-methoxyethanol was thoroughly degassed (2 hours) with N2 and heat. The solvent was then cooled to 70°C whereupon 5.0 g (4.02 mmol) tetrakistriphenylphosphine platinum (0), 2.34 g (4.02 mmol) imidazoliophane-Br and 2.22 g (16.1 mmol) potassium carbonate were added. The mixture was set to reflux for 15 minutes and then immediately cooled. The solution was filtered to give -0.9 g of white solid. Its filtrate was reduced to 50 mL via evaporation and enriched with 300 mL methanol. Another filtration gave an additional 0.37 g of white solid. These were combined and stirred in a mixture of water/methanol to solubilize any residual base and triphenylphoshine. A final filtration yielded 0.9 g of product. It was purified via high vacuum sublimation to give -0.7 g Pt (II) imidazoliophane as a white powdery solid as confirmed by MS and NMR (λmax = 486nm (DMF), Ox: 0.64V (i) vs. ferrocene, Red: not detectable, Tm: 491°C, Tg: not detectable).
Figure imgf000433_0001
Pt151
Synthesis of exemplary Iridium tris carbenes
Example 70: Synthesis of fac-iridium(III) tris (l-(2-naphthyl-3-methyl- benzimidazoline-2-ylidene- C,C?) and mer-iridium(III) tris (l-(2-naphthyl-3-methyl- benzimidazoline-2-ylidene-C, C2)
[0635] A 3 L round-bottomed flask was charged with 113.83 g of silver(I) oxide, 38 g of l-(2-naphthyl)-3-methyl-benzimidazolate iodide, 9.1 g of iridium trichloride hydrate, and 2000 mL of 2-ethoxyethanol. The reaction was stirred and heated at 120 °C for 2 hours under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure(20 mmHg). Filtration through Celite using dichloromethane as the eluent was performed to remove the silver(I) salts. A light brown solution was obtained and further purified by flash column chromatography on silica gel using dichloromethane as the eluent yielding 6 g (25.2%) of fac-iridium(III) tris (1- (2-naphthyl-3-methyl-benzimidazoline-2-ylidene-C,(7). The mer isomer was selectively crystallized from a mixture of dichloromethane and methanol. The mother liquid was evaporated to dryness and the residue was recrystallized from dichloromethane to obtain the fac isomer.
Example 71: Synthesis of Iridium (III) bis(l-phenyl-3-methyl-imidazoline-2-ylidene- C2) chloride dimer
[0636] A 2 L round-bottomed flask was charged with 80.87 g of silver(I) oxide, 10 g of l-phenyl-3-methyl-imidazolate iodide and 1 L of dichloromethane. The reaction was stirred at room temperature for 15 h under nitrogen while protected from light with aluminum foil. The reaction mixture was concentrated under reduced pressure. Filtration through Celite using dichloromethane as the eluent was performed to remove the silver(I) salts. The filtrate was concentrated to dryness and transferred to a 2 L round-bottomed flask by re- dissolving it in 2-(2-methoxyethoxy)ethanol (1000 mL). The reaction was stirred and heated to 185 °C under nitrogen. Iridium(III) trichloride hydrate (6.47 g) was added to the reaction mixture while the reaction temperature was maintained at 185 °C. The reaction mixture was stirred and heated for a further 5 hours at 185 °C. The reaction mixture was cooled to ambient temperature. Filtration through Celite using dichloromethane as the eluent was performed to remove the silver(I) salts. The solvent was removed under reduced pressure. The residue was purified by flash column chromatography on silica gel (30% ethyl acetate in dichloromethane) yielding 2.72 g (28.7%) of Iridium (III) bis(l-phenyl-3-methyl- imidazoline-2-ylidene- C.C2) chloride dimer.
Example 72: Synthesis of fac-iridium(III) tris (l-phenyl-3-methyl-benzimidazoline-2- ylidene- C2)
[0637] A 100 mL round-bottomed flask was charged with 740 mg of 1 -phenyl-3 - methyl-benzimidazoline iodide, 500 mg of Iridium(III) benzylpyridine dichloro bridged dimer, 470 mg of sodium carbonate and 100 mL of 2-ethoxyethanol. The reaction was stirred and heated at 135 °C for 3h under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure(20 mmHg). A light brown solution was obtained and further purified by flash column chromatography on silica gel using dichloromethane as the eluent yielding 540 mg (75%) of fac-iridium(III) tris(l -phenyl-3-methyl-benzimidazoline-2-ylidene-C, C2).
Example 73: Synthesis of f ac-iridium(III) tris (l-(4-fluorophenyl)-3-methyl- benzimidazoline-2-ylidene-C, C2)
[0638] A 100 mL round-bottomed flask was charged with 1.07 g of 1 -(4- fluorophenyl)-3-methyl-benzimidazoline iodide, 500 mg of Iridium(III) benzylpyridine dichloro bridged dimer, 470 mg of sodium carbonate and 100 mL of 2-ethoxyethanol. The reaction was stirred and heated at 135 °C for 3h under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure(20 mmHg). A light brown solution was obtained and further purified by flash column chromatography on silica gel using dichloromethane as the eluent yielding 500 mg (65%) of fac-iridium(III) tris (l-(4-fluorophenyl)-3-methyl- benzimidazoline-2-ylidene-C, C2). The pure fac isomer was obtained by recrystallization from methylene chloride.
Example 74: Synthesis of røer-tris(2-(4,6-difluoro-phenyl)pyridine)iridium (III)
[0639] A 100 mL round-bottomed flask was charged with 1 g of 2-(4,6-difluoro- phenyl)pyridine, lg of Iridium(III) benzylpyridine dichloro bridged dimer, 1.128 g of sodium carbonate and 100 mL of 2-ethoxyethanol. The reaction was stirred and heated at 135 °C for 3h under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure(20 mmHg). A light brown solution was obtained and further purified by flash column chromatography on silica gel using dichloromethane as the eluent yielding 1 g (74%) of pure er-tris(2-(4,6-difluoro- phenyl)pyridine)iridium (III).
Example 75: Synthesis of /«er-iridum(III) tris(diphenylbenzylphosphine)
[0640] A 100 mL round-bottomed flask was charged with 2.4 g of benzyl diphenyl phosphine, 1.4 g of benzylpyridine iridium(III) dichloro bridge dimer, 1.83 g of sodium carbonate and 100 mL of 2-ethoxyethanol. The reaction was stirred and heated at 135°C for 6h under nitrogen while protected from light with aluminum foil. The reaction mixture was cooled to ambient temperature and concentrated under reduced pressure(20mmHg). A light brown solution was obtained and further purified by flash column chromatography on silica gel using dichloromethane and hexanes mixture as the eluent yielding 2g (78%) of pure mer isomer was obtained.
[0641] While the present invention is described with respect to particular examples and preferred embodiments, it is understood that the present invention is not limited to these examples and embodiments. The present invention as claimed therefore includes variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art.

Claims

WHAT IS CLAIMED IS:
1. An organic light emitting device, comprising: (a) an anode; (b) a cathode; (c) an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound further comprising one or more carbene ligands coordinated to a metal center.
2. The device of claim 1, wherein the compound has the formula: z2 z 1 wherein Z and Z are selected from a carbon containing moiety , an amine containing moiety, oxygen containing moiety, a phosphine containing moiety, and a sulfur containing moiety.
3. The device of claim 2, wherein the compound has a structure selected from:
Figure imgf000436_0001
wherein M is a metal; the dotted lines represent optional double bonds; each Zi, A, and A' is independently selected from C, N, O, P, or S; Ri, R2, and R are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R\ C(O)NR'2, NR'2, NO2, OR', SR', SO , SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(0)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; (X-Y) is selected from a photoactive ligand or an ancillary ligand, α is O, 1, or 2. m is a value from 1 to the maximum number of ligands that may be attached to the metal; m + n is the maximum number of ligands that may be attached to metal M. 4. The device of claim 3, having the structure
Figure imgf000437_0001
wherein I?4 is selected from an aromatic or an amine group; and R3 and t together from independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J.
The device of claim 4, wherein the compound is selected from the group consisting of:
Figure imgf000437_0002
wherein R5 and Re are independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; and additionally or alternatively, one or more of RΪ and R2, R2 and R3, R3 and R5, and R5 and R together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J. 6. The device of claim 5, wherein the compound has the structure:
Figure imgf000438_0001
wherein R8, R , R10, and Rπ are independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR\ C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; and additionally or alternatively, one or more of R and R2, R2 and R8, R8 and R10, and R6 and Rio together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J.
7. The device of claim 6, wherein the compound is selected from the group consisting of:
Figure imgf000438_0002
wherein each R12 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR\ C(0)R\ C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R'5 halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R^ groups on adjacent ring atoms form a fused 5- or 6-membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; and dis O, 1 ,2 ,3 , or 4. The device of claim 7, wherein the compound has the structure:
Figure imgf000439_0001
wherein each R13 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(0)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R13 groups on adjacent ring atoms form a fused 5- or 6-membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; and c is 0, 1, 2, or 3. 9. The device of claim 3, wherein the compound is selected from the group consisting of:
Figure imgf000439_0002
wherein Z3 is independently selected from the group consisting of a C, O, S, P, or NR'; ring B is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M, wherein ring B can be optionally substituted with one or more substituents Rι ; and ring D is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M, wherein ring D can be optionally substituted with one or more substituents Rι5; and R1 and R15 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SiR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R groups on the same or adjacent ring atoms form a fused 5- or 6- membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; b is 0, 1, 2, 3, or 4.
10. The device of claim 9, wherein the compound has the structure:
Figure imgf000440_0001
Figure imgf000441_0001
11. The device of claim 10, wherein the compound is selected from the group consisting of:
Figure imgf000441_0002
12. The device of claim 11, wherein the compound has the structure:
Figure imgf000442_0001
wherein R6 is an alkyl or aryl group.
13. The device of claim 12, wherein M is selected from a group consisting of main group metals, 1st row transition metals, 2nd row transition metals, and 3rd row transition metals, and lanthanides.
14. The device of claim 13, wherein M is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.
15 The device of claim 14, wherein M is Ir. 16 The device of claim 15, wherein m is 3 and n is 0. 17 The device of claim 16, wherein R is methyl. 18 The device of claim 17, wherein m is 2. 19 The device of claim 18, wherein X-Y is selected from the group consisting of:
Figure imgf000442_0002
acetylacetonate, and picolinate. 20. The device of claim 11, wherein the compound is selected from the group consisting of:
Figure imgf000442_0003
Figure imgf000443_0001
The device of claim 20, wherein the compound is selected from the group consisting of:
Figure imgf000443_0002
Figure imgf000444_0001
Figure imgf000445_0001
2. The device of claim 21, wherein M is selected from a group consisting of main group metals, 1st row transition metals, 2nd row transition metals, and 3 rd row transition metals, and lanthanides.
23. The device of claim 22, wherein M is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.
24. The device of claim 23, wherein wherein M is Ir. 25. The device of claim 24, wherein m is 3 and n is 0. 26. The device of claim 24, wherein m is 2. 27. The device of claim 5, wherein the compound is selected from the group consisting of:
Figure imgf000446_0001
28. The device of claim 27, wherein the compound is selected from the group consisting of:
Figure imgf000446_0002
wherein ring B is an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M; and each Rι4 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR\ C(O)R\ C(O)NR' , NR' , NO2, OR', SR', SiR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R groups on the same or adjacent ring atoms form a fused 5- or 6- membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; b is 0, 1, 2, 3, or 4; and c is 0, 1, or 2. 29. The device of claim 28, wherein the compound is selected from the group consisting of:
Figure imgf000447_0001
wherein each R12 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN,
CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R groups on the same or adjacent ring atoms form a fused 5- or 6-membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J.
30. The device of claim 29, wherein the compound is selected from the group consisting of:
Figure imgf000448_0001
31. The device of claim 5, wherein the compound has the structure:
Figure imgf000448_0002
32. The device of claim 31, wherein the compound has the structure:
Figure imgf000448_0003
33. The device of claim 32, wherein the compound is selected from the group consisting of:
Figure imgf000448_0004
34. The device of claim 2, wherein the compound has the structure:
Figure imgf000448_0005
wherein Ri, R2, R3, R17, and Rι8 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; Rι6 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl;
Z4 and Z5 are independently selected from a bond, O, S, or NR'; Zls A, Ai, A', and A" is independently selected from C, N, or P;
(X-Y) is selected from a photoactive ligand or an ancillary ligand; a is 0, 1, or 2; c is 0, 1, 2, or 3; m is a value from 1 to the maximum number of ligands that may be attached to metal M; m + n is the maximum number of ligands that may be attached to metal M.
35. The device of claim 34, wherein the compound is selected from the group consisting of:
Figure imgf000449_0001
Figure imgf000449_0002
wherein R6, R1 , and Rι5 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; and b is 0, 1, 2, 3, or 4.
36. The device of claim 1, wherein M is selected from a group consisting of main group metals, 1st row transition metals, 2nd row transition metals, and 3 rd row transition metals, and lanthanides.
37. The device of claim 36, wherein M is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.
38. The device of claim 37, wherein n is zero and m is the maximum number of ligands that may be attached to metal M.
39. The device of claim 38, wherein M is Ir.
40. An organic light emitting device, comprising: (a) an anode; (b) a cathode; (c) an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound further comprising one or more ligands coordinated to a metal center, and at least one ligand is a zwitterionic carbon donor ligand.
41. The device of claim 40, wherein the compound is selected from the group consisting of:
Figure imgf000451_0001
Figure imgf000451_0002
wherein M is a metal; and
RΪ and R2 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; R3 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl;
(X-Y) is selected from a photoactive ligand or an ancillary ligand, a is 0, 1, 2, 3, or 4; b is 0, 1, 2, or 3; m is a value from 1 to the maximum number of ligands that may be attached to metal M; m + n is the maximum number of ligands that may be attached to metal M.
42. The device of claim 41, wherein M is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Al, Ga, Au, and Ag.
43. The device of claim 42, wherein M is Ir.
44. The device of claim 43, wherein m is 3 and n is 0.
45. A light emitting device, comprising:
(a) an anode; (b) a cathode; (c) an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a host and a dopant, and the host comprises a compound having at least one carbene atom coordinated to iridium, and the compound has the structure:
Figure imgf000452_0001
wherein the dotted lines represent optional double bonds; ring A is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to Ir, wherein ring A can be optionally substituted with one or more substituents Ra;
Ri is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; R2-R5, and Ra are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R or Ra groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(0)OR', C(0)R', C(O)NR' , NR'2, NO2, OR', SR', SO2, SOR', or SO3R\ and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; b is O, 1, 2, or 3.
46. The device of claim 45, wherein the compound has the structure:
Figure imgf000453_0001
47. The device of claim 46, wherein at least one of Rat and Ra3 is F.
48. The device of claim 47, wherein the compound has the structure:
Figure imgf000453_0002
49. The device of claim 46, wherein the compound has the structure:
Figure imgf000454_0001
wherein ring B is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring, wherein ring B can be optionally substituted with one or more substituents Rb;
Rb is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(0)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two Rb groups on the same ring together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; b is O, 1, 2, or 3.
50. The device of claim 49, wherein the compound is selected from the group consisting of:
Figure imgf000454_0002
Figure imgf000455_0001
51. The device of claim 45, wherein ring A comprises a nitrogen heteroatom.
52. The device of claim 51, wherein the compound has the structure:
Figure imgf000455_0002
wherein, additionally or alternatively, R3 and Rai and two adjacent Ra groups on the same ring together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J.
53. The device of claim 52, wherein the compound is selected from the group consisting of:
Figure imgf000455_0003
54. The device of claim 52, wherein the compound has the structure:
Figure imgf000456_0001
wherein ring C is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring, wherein ring C can be optionally substituted with one or more substituents Re;
Re is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two Re groups on the same ring together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; b is O, 1, 2, or 3.
55. The device of claim 54, wherein the compound is selected from the group consisting of:
Figure imgf000456_0002
Figure imgf000457_0001
56 An organic light emitting device, comprising: (a) an anode; (b) a cathode; (c) and at least one organic layer disposed between the anode and the cathode; the organic layer comprising a reversibly reducible metal complex of a redox active metal center and at least one ligand; wherein in a reduced state, an extra electron is localized on the metal center. 57. The device according to claim 56, wherein the metal complex is of Formula I
Figure imgf000457_0002
or Formula II
Figure imgf000457_0003
wherein is a redox active transition metal, E1 and E3 are independently selected from nitrogen, oxygen, and sulfur mono-anionic donors; E2 is a C, N, P, or Si neutral donor; (X-Y) is selected from a photoactive ligand or an ancillary ligand; m is a value from 1 to the maximum number of ligands that may be attached to metal Mi; and m + n is the maximum number of ligands that may be attached to metal Mi, such that the overall complex is neutral.
58. The device according to claim 56, wherein the metal is a d(0) metal.
59. The device according to claim 56, wherein the metal is Ti(IV).
60. The device according to claim 56, wherein the organic layer is an electron transporting layer.
61. The device according to claim 56, wherein the reversibly reducible metal complex is a host material.
62. The device according to claim 56, wherein at least one ligand of the complex is a carbene.
63. The device according to claim 56, wherein, in the reduced state, the ligand remains complexed to the metal.
64. The device according to claim 56, wherein the reversibly reducible metal complex is neutral in the resting state.
65. The device according to claim 56, wherein the reversibly reducible metal complex is substantially colorless in the resting state.
66. The device according to claim 56, wherein the reversibly reducible metal complex has an extinction coefficient of no more than about 1000 M'Am"1 at wavelengths from about 400nm to about 750 nm in the resting state.
67. The device according to claim 56, wherein a ligand is selected from the group consisting of
Figure imgf000459_0001
Figure imgf000459_0002
Figure imgf000459_0003
Figure imgf000459_0004
where E1 and E3 are either/or nitrogen, oxygen, or sulfur mono anionic donors, and E2 is a C, N, P, or Si neutral donor,
Figure imgf000460_0001
Figure imgf000460_0002
68. The device according to claim 56, wherein the reversibly reducible metal complex is selected from the group consisting of:
Figure imgf000460_0003
Figure imgf000461_0001
1 where E and E are either/or nitrogen, oxygen, or sulfur mono anionic donors, and E is a C, N, P, or Si neutral donor,
Figure imgf000461_0002
69. A reversibly reducible metal complex, selected from the group consisting of complexes of formula:
Figure imgf000462_0003
Figure imgf000462_0002
Figure imgf000463_0001
where E and E are either/or nitrogen, oxygen, or sulfur mono anionic donors, E2 is a C, N, P, Si, etc neutral donor,
Figure imgf000463_0002
Figure imgf000464_0001
Figure imgf000464_0005
Figure imgf000464_0004
Figure imgf000464_0002
Figure imgf000464_0003
70. A host or electron transporting material, comprising the reversibly reducible metal complex according to claim 69.
71. An organic light emitting device, comprising: (a) an anode; (b) a cathode; and (c) an emissive region disposed between the anode and the cathode, wherein the emissive region comprises an emissive complex that further comprises one or more carbene ligands coordinated to a metal center, wherein the complex is cationic.
72. The organic light emitting device of claim 71, wherein the metal center is selected from Re, Ru, Os, Rh, Ir, Pd, Pt, or Au.
73. The organic light emitting device of claim 72, wherein the emissive complex further comprises one or more carbon-metal bonds to the metal center wherein the further carbon-metal bonds are non-carbene-metal bonds.
74. The organic light emitting device of claim 73, wherein the one or more non-carbene carbon-metal bonds are phenyl-metal bonds.
75. The organic light emitting device of claim 72, wherein the device emits with a λmsκ less than about 450 nm.
76. The organic light emitting device of claim 75, wherein the device emits with a λmax less than about 500 nm.
77. The organic light emitting device of claim 72, wherein the device emits light having CIE coordinates wherein the X-coordinate is from about 0.10 to about 0.15, and the Y- coordinate in from about 0.10 to about 0.20.
78. The organic light emitting device of claim 72, wherein the compound has a structure selected from:
Figure imgf000465_0001
c9 dO c11
Figure imgf000466_0001
and
79. An organic light emitting device, comprising: (a) an anode; (b) a cathode; and (c) a phosphorescent emissive region disposed between the anode and the cathode, wherein the emissive region comprises an emissive material having the formula III:
Figure imgf000467_0001
wherein:
M is a second or third row transition metal; the dotted lines represent optional double bonds;
L is an ancillary ligand;
X1 is selected from C and N;
X2 is selected from C, N, O, S and P;
X3 is selected from C and N; each Q is independently selected from a chemical bond and -C(R')2-;
Y s C orN;
Y2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N;
R1 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; a is 1 or 2;
R3 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; c is 1 or 2; alternatively, R1 and R3, taken together with Y1 and Y2, form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; z s C orN;
Z2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N;
R2 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; b is 1 or 2;
R4 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(0)NR'2, aryl and heteroaryl; dis 1 or 2; alternatively, R2 and R4, taken together with Z1 and Z2, form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R\ C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl;
R5 and R6 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; or alternatively, R5 and R6, taken together with X1, X2 and X3 form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R1 and R5 taken together with X1, Q and Y1 form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR\ C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R and R taken together with X , Q and Z form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; n is 1 or 2; and m is 0 to 3, wherein when n is 1, m is 1 to 3, and when n is 2, m is 0; wherein at least one of X2, Y2 or Z2 is C and is selected to be a carbene donor. 80 The device of claim 79, wherein M is selected from Ru, Os, Re, Rh, Ir, Pd and Pt. 81 The device of claim 80, wherein M is selected from Os and Ru. 82 The device of claim 81, wherein M is Os. 83 The device of claim 79, wherein the emissive material comprises a neutral compound. 84 The device of claim 79, wherein the emissive material comprises a charged compound. 85 The device of claim 79, wherein the emissive material has the formula IV:
Figure imgf000469_0001
wherein:
M is a second or third row transition metal; the dotted lines represent optional double bonds;
L is an ancillary ligand;
X1 is selected from C and N;
X2 is selected from C, N, O, S and P;
X3 is selected from C and N; ring A selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, wherein ring A may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each Q is independently selected from a chemical bond and -C(R')2-;
Y^s C or N;
Y2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N;
R1 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(0)NR'2, aryl and heteroaryl; a is 1 or 2; R3 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; c is 1 or 2; alternatively, R1 and R3, taken together with Y1 and Y2, form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; zMs C or N;
Z2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N;
R2 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; b is 1 or 2;
R4 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; d is 1 or 2; alternatively, R2 and R4, taken together with Z1 and Z2, form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; n is 1 or 2; m is 0 to 3, wherein when n is 1, m is 1 to 3, and when n is 2, m is 0; and wherein at least one of X2, Y2 or Z2 is C and is selected to be a carbene donor.
86. The device of claim 85, wherein M is selected from Ru, Os, Re, Rh, Ir, Pd and Pt.
87. The device of claim 86, wherein M is selected from Os and Ru.
88. The device of claim 87, wherein M is Os.
89. The device of claim 85, wherein the emissive material has the formula V:
Figure imgf000471_0001
wherein
M is a second or third row transition metal; the dotted lines represent optional double bonds;
X1 is selected from C and N;
X2 is selected from C, N, O, S and P;
X is selected from C and N; ring A selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, wherein ring A may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each Q is independently selected from a chemical bond and -C(R')2-;
Y s C or N;
Y2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N;
R1 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; a is 1 or 2;
R3 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; c is 1 or 2; alternatively, R1 and R3, taken together with Y1 and Y2, form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl;
Figure imgf000472_0001
Z2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N;
R2 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; b is 1 or 2;
R4 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; dis 1 or 2; alternatively, R2 and R4, taken together with Z1 and Z2, form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R1 and R5 taken together with X1, Q and Y1 form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R2 and R6 taken together with X3, Q and Z1 form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; and wherein at least one of X2, Y2 or Z2 is C and is selected to be a carbene donor.
90. The device of claim 89, wherein M is selected from Ru, Os, Re, Rh, Ir, Pd and Pt.
91. The device of claim 90, wherein M is selected from Os and Ru.
92. The device of claim 91 , wherein M is Os.
93. The device of claim 79, wherein the emissive material has the formula VI:
Figure imgf000473_0001
wherein
M is a second or third row transition metal; the dotted lines represent optional double bonds;
X1 is selected from C and N;
X2 is selected from C and N;
X3 is selected from C and N;
Y s C orN;
Y2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N;
R1 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; a is 1 or 2; R3 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; c is 1 or 2; alternatively, R1 and R3, taken together with Y1 and Y2, form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; z s C orN;
Z2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N; R2 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl; b is 1 or 2;
R4 is selected from H, alkyl, alkenyl, alkynyl, aralkyl, C(O)R', C(O)OR', C(O)NR'2, aryl and heteroaryl;
<iis 1 or 2; alternatively, R2 and R4, taken together with Z1 and Z2, form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl;
R7, R8 and R9 are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively, R5 and R6 or R6 and R7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO , SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R1 and R7 taken together with the atoms to which they are attached form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R2 and R9 taken together with the atoms to which they are attached form a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; and wherein at least one of X2, Y2 or Z2 is C and is selected to be a carbene donor.
94. The device of claim 93, wherein M is selected from Ru, Os, Re, Rh, Ir, Pd and Pt.
95. The device of claim 94, wherein M is selected from Os and Ru.
96. The device of claim 95, wherein M is Os.
97. The device of claim 79, wherein the emissive material has the formula VII:
Figure imgf000475_0001
wherein:
M is a second or third row fransition metal; the dotted lines represent optional double bonds;
L is an ancillary ligand;
X1 is selected from C and N;
X2 is selected from C and N;
X3 is selected from C and N; ring A selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, wherein ring A may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; ring B and ring C are independently selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each Q is independently selected from a chemical bond and -C(R')2-;
Y^s C orN;
Y2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N; z s C or N;
Z2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N; each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; n is 1 or 2; m is 0 to 3, wherein when n is 1, m is 1 to 3, and when n is 2, m is 0; and wherein at least one of X2, Y2 or Z2 is C and is selected to be a carbene donor.
98. The device of claim 97, wherein M is selected from Ru, Os, Re, Rh, Ir, Pd and Pt.
99. The device of claim 98, wherein M is selected from Os and Ru.
100. The device of claim 99, wherein M is Os.
101. The device of claim 79, wherein the emissive material has the formula VIII:
Figure imgf000476_0001
wherein:
M is a second or third row transition metal; the dotted lines represent optional double bonds;
L is an ancillary ligand;
X1 is selected from C and N;
X2 is selected from C and N;
X3 is selected from C and N; ring B and ring C are independently selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each Q is independently selected from a chemical bond and -C(R')2-; Y s C or N;
Y2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N; z s C or N;
Z2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N;
R7, R8 and R9 are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively, R5 and R6 or R6 and R7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; π is 1 or 2; m is 0 to 3, wherein when n is 1, m is 1 to 3, and when n is 2, m is 0; and wherein at least one of X2, Y2 or Z2 is C and is selected to be a carbene donor..
102. The device of claim 101, wherein M is selected from Ru, Os, Re, Rh, Ir, Pd and Pt.
103. The device of claim 102, wherein M is selected from Os and Ru.
104. The device of claim 103, wherein M is Os.
105. The device of claim 79, wherein the emissive material has the formula IX:
Figure imgf000477_0001
wherein:
M is a second or third row transition metal; the dotted lines represent optional double bonds; L is an ancillary ligand; X1 is selected from C and N;
X2 is selected from C and N;
X3 is selected from C and N; ring B and ring C are independently selected from a 5- or 6- membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(0)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each Q is independently selected from a chemical bond and -C(R')2-;
Y s C or N;
Y2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N; z s C orN;
Z2 is C, N, O, S or P, wherein when Y1 is N, Y2 is C or N;
R7, R8 and R9 are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively, R5 and R6 or R6 and R7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl; and wherein at least one of X2, Y2 or Z2 is C and is selected to be a carbene donor.
106. The device of claim 105, wherein M is selected from Ru, Os, Re, Rh, Ir, Pd and Pt.
107. The device of claim 106, wherein M is selected from Os and Ru.
108. The device of claim 107, wherein M is Os.
109. The device of claim 79, wherein the emissive material has the formula X:
Figure imgf000479_0001
wherein:
M is a second or third row fransition metal;
X is selected from C or N;
Q is a bond or -C(R*)2-;
R7, R8 and R9 are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively, R and R6 or R6 and R7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl;
R12 is selected from alkyl, aryl and aralkyl;
R10 and R11 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R10 and R11, or R11 and R12 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl;
R22 is selected from alkyl, aryl and aralkyl;
R20 and R21 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively R20 and R21, or R21 and R22 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(0)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl.
110. The device of claim 109, wherein M is selected from Ru, Os, Re, Rh, Ir, Pd and Pt.
111. The device of claim 110, wherein M is selected from Os and Ru.
112. The device of claim 111, wherein M is Os.
113. The device of claim 79, wherein the emissive material has the formula XI:
Figure imgf000480_0001
wherein
M is a second or third row transition metal;
X2 is selected from C or N;
R7, R8 and R9 are independently selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2,
SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively, R5 and R6 or R6 and R7 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group optionally contains 1 to 3 ring heteroatoms and is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2,
SOR', or SO3R' halo, aryl and heteroaryl; R12 is selected from alkyl, aryl and aralkyl;
R10 and R11 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2,
SR', C(0)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R10 and R11, or R11 and R12 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2,
CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl;
R22 is selected from alkyl, aryl and aralkyl;
R20 and R21 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2,
SR', C(0)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively R and R , or R and R form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2,
CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl.
114. The device of claim 113, wherein M is selected from Ru, Os, Re, Rh, Ir, Pd and Pt.
115. The device of claim 114, wherein M is selected from Os and Ru.
116. The device of claim 115, wherein M is Os.
117. The device of claim 79, wherein the emissive material has the formula XII:
Figure imgf000481_0001
wherein: M is a second or third row transition metal;
Y2 and Z2 are independently selected from C and N;
R8, R9, R13, R14, R15, R16, R23, R24, R25, and R26 are independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R8 and R9 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; additionally or alternatively R13 and R14, or R14 and R15, or R15 and R16 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and additionally or alternatively R23 and R24, or R24 and R25, or R25 and R26 form a fused 5- or 6- membered cyclic group, wherein the fused cyclic group is optionally substituted with one of more substituents selected from alkyl, alkenyl, alkynyl, aralkyl, O-R', N(R')2, SR', C(O)R% C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', or SO3R' halo, aryl and heteroaryl; and each R' is independently selected from H, alkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl.
118. The device of claim 117, wherein M is selected from Ru, Os, Re, Rh, Ir, Pd and Pt.
119. The device of claim 118, wherein M is selected from Os and Ru.
120. The device of claim 119, wherein M is Os.
121. An organic light emitting device, comprising: (a) an anode; (b) a cathode; (c) an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound further comprising one or more carbene atoms coordinated to a d metal.
122. The device of claim 121, wherein the metal is Pt(II), Pd(II), Ir(I), Au(III), or Rh(I).
123. The device of claim 122, wherein the metal is Pt(II).
124. An organic light emitting device, comprising: (a) an anode; (b) a cathode; (c) and a phosphorescent emissive region disposed between the anode and the cathode, wherein the emissive region comprises an emissive material having a structure XVII:
Figure imgf000483_0001
wherein: M is a metal; W, X, Y, and Z are independently a group containing C, N, P, O, or S coordinated to the metal M; at least one of W, X, Y, or Z is coordinated to the metal by a carbene donor; L1, L2, L3, and L4 are independently a linking group; x can be 0 or 1.
125. The device of claim 124, wherein the emissive material has a structure XVIII:
Figure imgf000483_0002
XVIII wherein: M is Pt or Pd; the dotted lines represent optional double bonds; 1, W3, X1, X3, Y1, Y3, Z1, and Z3 are independently C or N; W2, X2, Y2, and Z2 are independently C, N, O, S or P; wherein at least one of W2, X2, Y2 and Z2 is a carbene; wherein for each group W, X, Y, and Z at least one of atoms 1, 2, and 3 is C; L1, L2, and L3 are independently a linking group; R7 and R8 may optionally be joined to form a linking group L4; R1"10 are independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, heteroaryl, C(O)R', C(O)OR', or C(O)NR'2; each of R1 and R2, R3 and R4, R5 and R6, and R9 and R 10, taken together with the atoms of groups X, Y, Z, and , respectively, can independently and optionally can form a 5- or 6- member cyclic group or an 8- to 10-membered fused bicyclic group, which may be optionally substituted by one or more substituents J; each substituent J is independently R', O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, CF3, NO2, SO2, SOR', SO3R', or halo, and any two J groups on adjacent ring atoms can optionally form a 5- or 6-member cyclic group; and each R' is independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, or heteroaryl.
126. The device of claim 125, wherein the emissive material has a structure XIX:
Figure imgf000484_0001
wherein L4 is a linking group.
127. The device of claim 125, wherein the emissive material has a structure XX:
Figure imgf000484_0002
XX wherein A and B are independently a 5- or 6-membered cyclic group or a 8- to 10-membered fused bicyclic group, which may be optionally substituted with one or more substituents J
128. The device of claim 127, wherein the emissive material has a structure XXI:
Figure imgf000485_0001
XXI wherein A, B, C, and D are independently a 5- or 6-membered cyclic group or a 8- to 10- membered fused bicyclic group, which may be optionally substituted with one or more substituents J. 129. The device of claim 128, wherein the emissive material has a structure XXII:
Figure imgf000485_0002
XXII wherein L4 is a linking group.
130. The device of claim 128, wherein all of the rings A, B, C, and D are aromatic rings.
131. The device of claim 128, wherein two of the rings A, B, C, and D are imidazoie rings, and each of the remaining two rings is a phenyl ring or a pyridyl ring.
132. The device of claim 131, wherein the emissive material has a structure XXIII:
Figure imgf000485_0003
wherein: 9 "J W and Z are independently C or N; L2 is a linking group; R28 and R29 may optionally be joined to form a linking group L4; R20"32 are independently a substituent J. 133. The device of claim 132, wherein the emissive material has a structure XXIV:
Figure imgf000486_0001
wherein L4 is a linking group. 134. The device of claim 131, wherein the emissive material has a structure XXV:
Figure imgf000486_0002
wherein: X2 and Z2 are independently C or N; L1, L2, L3, and L4 are independently a linking group; R40'49 are independently a substituent J.
135. An organic light emitting device, comprising: (a) an anode; (b) a cathode; (c) an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound further comprising a metal coordinated to: i) one or more carbene donors; ii)- 0-3 neutral donors; and iii) 0-3 monoanionic donors; wherein the total number of donors is the maximum number of ligands that may be attached to the metal, and wherein each donor is optionally linked to one or more adjacent donors.
136. The device of claim 135, wherein the donors are linked to form a macrocyclic ligand.
137. The device of claim 136, wherein each interplanar angle of the macrocyclic ligand is less than about 15°.
138. The device of claim 137, wherein each interplanar angle is less than about 10°.
139. The device of claim 138, wherein each interplanar angle is about 0°.
140. The device of claim 136, wherein the metal is coordinated to 4 donors, and the donors are linked to form a tetradentate ligand.
141. The device of claim 135, wherein the metal is coordinated to : a) one or more carbene donor, wherein each carbene donor is selected from the group consisting of:
Figure imgf000487_0001
Figure imgf000487_0002
Figure imgf000488_0001
b) 0-3 neutral donors, wherein each neutral donor is selected from the group consisting of:
Figure imgf000488_0002
and c) 0-3 monoanionic donors, wherein each monoanionic donor is selected from the group consisting of:
Figure imgf000488_0003
wherein each donor is optionally linked to one or more adjacent donors; and wherein each donor is optionally substituted with one or more substitutents J; each substituent J is independently R', O-R',.N(R')2, SR', C(O)R', C(O)OR', C(O)NR'2, CN, O2, SO2, SOR', or SO3R', and any two J groups on adjacent ring atoms can optionally form a 5- or 6-member aromatic group; each R' is independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, or heteroaryl.
142. The device of claim 141, wherein the metal forms a carbon-metal bond with at least one carbon atom that is not a carbene donor.
143. The device of claim 142, wherein the metal forms a carbon-metal bond with a phenyl group.
144. The device of claim 143, wherein the metal is coordinated to two carbene donors and two phenyl groups.
145. The device of claim 141, wherein the metal is coordinated to two bidentate ligands.
146. The device of claim 141 , wherein the metal is coordinated to one tridentate ligand and one monodentate ligand.
147. The device of claim 141 , wherein the metal is coordinated to a tetradentate ligand.
148. The device of claim 141, wherein at least one ligand has a triplet energy corresponding to a wavelength of less than 450 nm.
149. The device of claim 141, wherein the compound is selected from the group consisting of:
Figure imgf000489_0001
Figure imgf000490_0001
Figure imgf000491_0001
150. An organic light emitting device comprising: a) an anode; b) a cathode; c) an organic layer disposed between the anode and the cathode, wherein the organic layer comprises an organometallic compound further comprising a macrocyclic ligand coordinated to a metal center, wherein each interplanar angle of the macrocyclic ligand is less than about 15°.
151. The device of claim 150, wherein each interplanar angle is less than about 10°.
152. The device of claim 151, wherein each interplanar angle is about 0°.
153. The device of claim 150, wherein the macrocyclic ligand is a tetradentate ligand.
154. The device of claim 153, wherein the tetradentate ligand comprises two 5-membered rings and two 6-membered rings, each ring coordinated to the metal center.
155. The device of claim 1, wherein the compound has a structure XIII:
Figure imgf000492_0001
wherein M is a metal; A is C or N; Zi is C or N; R1, R2, R3, and R4 are independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, heteroaryl, C(O)R', C(O)OR', or C(O)NR'2; and each of R1 and R2, R2 and R3, and R3 and R4 independently and optionally can form a 5- or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently R, O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR2,
CN, CF3, NO2, SO2, SOR', SO3R', or halo, and any two J groups on adjacent ring atoms can optionally form a 5- or 6-member cyclic group; each R' is independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, or heteroaryl; Q is an ancillary ligand; n is a value from 2 to the maximum number of ligands that may be attached to metal M; m + n is the maximum number of ligands that may be attached to metal M.
156. The device of claim 155, wherein M is Ir, Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, or Ag.
157. The device of claim 155, wherein n is 2 and m is 0.
158. The device of claim 157, wherein the compound has a structure XV:
Figure imgf000493_0001
wherein M is Pt or Pd;
Figure imgf000493_0002
the phenyl groups may be optionally substituted with one or more substituents J.
159. The device of claim 157, wherein the compound has a structure XVI:
Figure imgf000493_0003
wherein M is Pt or Pd; Z2 is C or Si; and the phenyl groups may be optionally substituted with one or more substituents J.
160. The device of claim 150, wherein the compound further comprises a carbene donor.
161. The device of claim 160, wherein the compound is selected from the group consisting of:
Figure imgf000493_0004
162. A organometallic tetradentate compound, wherein each interplanar angle is less than about 15°, and having a structure XIV:
Figure imgf000494_0001
wherein M is a metal; A is C or N; Z\ is C orN; R1, R2, R3, and R4 are independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, heteroaryl, C(O)R', C(O)OR, or C(O)NR'2; and each of R1 and R2, R2 and R3, and R3 and R4 independently and optionally can fonn a 5- or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently R', O-R', N(R')2, SR', C(O)R', C(O)OR', C(O)NR2,
CN, CF3, NO2, SO2, SOR', SO R', or halo, and any two J groups on adjacent ring atoms can optionally form a 5- or 6-member cyclic group; each R is independently H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, or heteroaryl;
163. The compound of claim 162 having a structure XV:
Figure imgf000494_0002
wherein M is Pt or Pd; Z2 is C or Si; and the phenyl groups may be optionally substituted with one or more substituents J.
164. The compound of claim 162 having a structure XVI:
Figure imgf000495_0001
wherein M is Pt or Pd; Z2 is C or Si; and the phenyl groups may be optionally substituted with one or more substituents J.
165. An organic light emitting device, comprising: (a) an anode; (b) a cathode; (c) an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a carbene ligand.
166. The device of claim 165, wherein the ligand has the formula: z2 ZA wherein Z1 and Z2 are selected from a carbon containing moiety, an amine containing moiety, oxygen containing moiety, a phosphine containing moiety, and a sulfur containing moiety.
167. The device of claim 166, wherein the ligand has a structure selected from:
Figure imgf000495_0002
wherein the dotted lines represent optional double bonds; each Zi, A, and A' is independently selected from C, N, O, P, or S; Ri, R2, and R3 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl;and a is 0, 1, or 2. 168. The device of claim 167, having the structure
Figure imgf000496_0001
wherein 1^ is selected from an aromatic or an amine group; and R3 and R4 together from independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J. 169. The device of claim 168, wherein the ligand is selected from the group consisting of:
Figure imgf000496_0002
wherein R5 and R6 are independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; and additionally or alternatively, one or more oiRi and R2, R2 and R3, R3 and R5, and R5 and Rδ together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J. 170. The device of claim 169, wherein the ligand has the structure:
Figure imgf000497_0001
wherein R8, R9, R10, and Rπ are independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR\ C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; and additionally or alternatively, one or more of Ri and R2, R2 and R8, R8 and R10, and R6 and R10 together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J. 171. The device of claim 170, wherein the ligand is selected from the group consisting of:
Figure imgf000497_0002
wherein each R12 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R^ groups on adjacent ring atoms form a fused 5- or 6-membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; and dis 0, 1 ,2 ,3 , or 4. 172. The device of claim 171, wherein the ligand has the structure:
Figure imgf000498_0001
wherein each R13 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R13 groups on adjacent ring atoms form a fused 5- or 6-membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; and c is 0, 1, 2, or 3. 173. The device of claim 167, wherein the ligand is selected from the group consisting of:
Figure imgf000498_0002
Figure imgf000499_0001
wherein
Z3 is independently selected from the group consisting of a C, O, S, P, or NR'; ring B is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M, wherein ring B can be optionally substituted with one or more substituents Rι4; and ring D is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M, wherein ring D can be optionally substituted with one or more substituents Rι5; and
Rι4 and R15 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SiR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R groups on the same or adjacent ring atoms form a fused 5- or 6- membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; b is O, 1, 2, 3, or 4.. The device of claim 173, wherein the ligand has the structure:
Figure imgf000499_0002
Figure imgf000500_0001
175. The device of claim 174, wherein the ligand is selected from the group consisting of:
Figure imgf000500_0002
176. The device of claim 175, wherein the ligand has the structure:
Figure imgf000500_0003
wherein R^ is an alkyl or aryl group. 177. The device of claim 176, wherein Re is methyl. 178. The device of claim 177, wherein the ligand is selected from the group consisting of:
Figure imgf000501_0001
179. The device of claim 178, wherein the ligand is selected from the group consisting of:
Figure imgf000501_0002
Figure imgf000502_0001
Figure imgf000502_0002
Figure imgf000503_0001
180. The device of claim 169, wherein the ligand is selected from the group consisting of:
Figure imgf000503_0002
181. The device of claim 180, wherein the ligand is selected from the group consisting of:
Figure imgf000503_0003
wherein ring B is an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring; and each Rι4 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO , OR', SR', SiR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R groups on the same or adjacent ring atoms form a fused 5- or 6- membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; b is 0, 1, 2, 3, or 4; and c is 0, 1, or 2. 182. The device of claim 181, wherein the ligand is selected from the group consisting of:
Figure imgf000504_0001
183. The device of claim 182, wherein the ligand is selected from the group consisting of:
Figure imgf000504_0002
184. The device of claim 169, wherein the ligand has the structure:
Figure imgf000504_0003
185. The device of claim 184, wherein the ligand has the structure:
Figure imgf000505_0001
186. The device of claim 185, wherein the ligand has the structure:
Figure imgf000505_0002
187. The device of claim 166, wherein the ligand has the structure:
Figure imgf000505_0003
wherein Rls R2, R3, R17, and R18 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; R16 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(0)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; Z4 and Z5 are independently selected from a bond, O, S, or NR'; Zi, A, Ai, A', and A" is independently selected from C, N, or P; (X-Y) is selected from a photoactive ligand or an ancillary ligand; a is 0, 1, or 2; c is 0, 1, 2, or 3. 188. The device of claim 187, wherein the ligand is selected from the group consisting of:
Figure imgf000506_0001
wherein Re, Rι4, and Rι5 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR' , NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; and b is 0, 1, 2, 3, or 4. 189. An organic light emitting device, comprising: (a) an anode; (b) a cathode; (c) an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a zwitterionic carbon donor ligand. 190. The device of claim 189, wherein the compound is selected from the group consisting of:
Figure imgf000507_0001
wherein Ri and R2 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R\ C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; R3 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; a is 0, 1, 2, 3, or 4; b is 0, 1, 2, or 3.
191. A light emitting device, comprising :
(a) an anode; (b) a cathode; (c) an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a host and a dopant, and the host comprises a compound having at least one carbene atom coordinated to iridium, and the compound has the structure:
Figure imgf000508_0001
wherein the dotted lines represent optional double bonds; ring A is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to Ir, wherein ring A can be optionally substituted with one or more substituents Ra;
Ri is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; R2- 5, and Ra are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R or Ra groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF , C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; and b is 0, 1, 2, or 3.
192. The device of claim 191, wherein the ligand has the structure:
Figure imgf000509_0001
193. The device of claim 192, wherein at least one of Rai and Ra3 is F. 194. The device of claim 193, wherein the ligand has the structure:
Figure imgf000509_0002
195. The device of claim 192, wherein the ligand has the structure:
Figure imgf000509_0003
wherein ring B is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring, wherein ring B can be optionally substituted with one or more substituents Rb;
Rb is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two Rb groups on the same ring together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R\ C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; b is 0, 1, 2, or 3.
196. The device of claim 195, wherein the ligand is selected from the group consisting of:
Figure imgf000510_0001
197. The device of claim 191, wherein ring A comprises a nitrogen heteroatom. 198. The device of claim 197, wherein the ligand has the structure:
Figure imgf000510_0002
wherein, additionally or alternatively, R3 and Rai and two adjacent Ra groups on the same ring together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J. 199. The device of claim 198, wherein the ligand is selected from the group consisting of:
Figure imgf000510_0003
200. The device of claim 198, wherein the ligand has the structure:
Figure imgf000511_0001
wherein ring C is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring, wherein ring C can be optionally substituted with one or more substituents Re;
Re is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF , CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two Re groups on the same ring together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; b is 0, 1, 2, or 3.
201. The device of claim 200, wherein the ligand is selected from the group consisting of:
Figure imgf000511_0002
202. An organic light emitting device, comprising: (a) an anode; (b) a cathode; (c) a phosphorescent emissive layer, disposed between the anode and the cathode, including a phosphorescent emissive material having a highest energy peak wavelength less than 450 nm.
203. The device of claim 202, wherein the phosphorescent emissive material has a highest energy peak wavelength less than 440 nm.
204. The device of claim 202, wherein the phosphorescent emissive material has a highest energy peak wavelength less than 390 nm.
205. The device of claim 202, wherein the device emits at room temperature.
206. An organic light emitting device, comprising: (a) an anode; (b) a cathode; (c) a phosphorescent emissive layer, disposed between the anode and the cathode, wherein at least 45 % of the integral of the curve for the normalized elecfroluminescent specfra of the device is at a wavelength less than 450.
207. The device of claim 206, wherein at least 45 % of the integral of the curve for the normalized electroluminescent spectra of the device is at a wavelength less than 440 nm
208. The device of claim 207, wherein at least 45 % of the integral of the curve for the normalized electroluminescent spectra of the device is at a wavelength less than 390 nm.
209. A compound selected from the group consisting of:
Figure imgf000512_0001
wherein A is independently selected from C, N, O, P, or S; Z3 is independently selected from the group consisting of a C, O, S, P, or NR'; ring B is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M, wherein ring B can be optionally substituted with one or more substituents Rι4; and ring D is independently an aromatic cyclic, heterocyclic, fused cyclic, or fused heterocyclic ring with at least one carbon atom coordinated to metal M, wherein ring D can be optionally substituted with one or more substituents Rι5; and Rι4 and R15 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SiR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R groups on the same or adjacent ring atoms form a fused 5- or 6- membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; b is O, 1, 2, 3, or 4. 210. The compound of claim 209, wherein the compound is selected from the group consisting of:
Figure imgf000513_0001
211. The compound of claim 209, wherein the compound has the structure:
Figure imgf000513_0002
212. The compound of claim 211, wherein the compound is selected from the group consisting of:
Figure imgf000514_0002
213. The compound of claim 212, wherein the compound has the structure :
Figure imgf000515_0001
wherein R6 is an alkyl or aryl group.
214. The compound of claim 213, wherein M is selected from a group consisting of main group metals, 1st row transition metals, 2nd row transition metals, and 3 rd row transition metals, and lanthanides.
215. The compound of claim 214, wherein M is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.
216. The compound of claim 215, wherein M is Ir.
217. The compound of claim 216, wherein m is 3 and n is 0.
218. The compound of claim 217, wherein Re is methyl.
219. The compound of claim 218, wherein m is 2.
220. The compound of claim 219, wherein X-Y is selected from the group consisting of:
Figure imgf000515_0002
acetylacetonate, and picolinate. 221. The compound of claim 212, wherein the compound is selected from the group consisting of:
Figure imgf000516_0001
222. The compound of claim 221, wherein the compound is selected from the group consisting of:
Figure imgf000517_0001
Figure imgf000518_0001
517
Figure imgf000519_0001
223. The compound of claim 222, wherein M is selected from a group consisting of main group metals, 1st row transition metals, 2nd row transition metals, and 3 rd row transition metals, and lanthanides.
224. The compound of claim 223, wherein M is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.
225. The compound of claim 224, wherein wherein M is Ir. 226. The compound of claim 225, wherein m is 3 and n is 0. 227. The compound of claim 226, wherein m is 2. 228. The compound of claim 210, wherein the compound is selected from the group consisting of:
Figure imgf000519_0002
229. The compound of claim 228, wherein the compound is selected from the group consisting of:
Figure imgf000519_0003
230. The compound of claim 229, wherein the compound is selected from the group consisting of:
Figure imgf000520_0001
wherein each R12 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3 C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl and heteroaryl; or alternatively, two R groups on the same or adjacent ring atoms form a fused 5- or 6-membered cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J. 231. The compound of claim 230, wherein the compound is selected from the group consisting of:
Figure imgf000521_0001
232. The compoxmd of claim 231, wherein M is selected from a group consisting of main group metals, 1st row transition metals, 2nd row transition metals, and 3rd row transition metals, and lanthanides.
233. The compound of claim 232, wherein M is selected from the group consisting of Ir, Pt, Pd, Rh, Re, Ru, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and Ag.
234. The compound of claim 233, wherein n is zero and m is the maximum number of ligands that may be attached to metal M.
235. The compound of claim 234, wherein M is Ir. 236. The compound of claim 210, wherein the compound has the structure:
Figure imgf000521_0002
237. The compound of claim 236, wherein the compound is selected from the group consisting of:
Figure imgf000521_0003
238. A compound comprising one or more carbene ligands coordinated to a metal center, wherein the compound has the structure:
Figure imgf000522_0001
wherein Ri, R2, R3, R1 , and Rι8 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; R16 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl;
Z4 and Z5 are independently selected from a bond, O, S, or NR'; Z\, A, Ai, A', and A" is independently selected from C, N, or P;
(X-Y) is selected from a photoactive ligand or an ancillary ligand; a is 0, 1, or 2; c is 0, 1, 2, or 3; m is a value from 1 to the maximum number of ligands that may be attached to metal M; m + n is the maximum number of ligands that may be attached to metal M.
239. The compound of claim 238, wherein the compound is selected from the group consisting of:
Figure imgf000523_0002
Figure imgf000523_0004
Figure imgf000523_0001
wherein R6, R14, and R15 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2> NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl; and b is 0, 1, 2, 3, or 4.
240. A compound comprising one or more carbene ligands coordinated to a metal center, and at least one ligand is a zwitterionic carbon donor ligand, and wherein the compound is selected from the group consisting of:
Figure imgf000523_0003
Figure imgf000524_0001
Figure imgf000524_0002
wherein M is a metal; and
Ri and R2are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, CN, CF3, CO2R', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', SO3R', halo, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; R3 is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a heterocyclic group; and additionally or alternatively, two R groups on the same or adjacent ring, together form independently a 5 or 6-member cyclic group, wherein said cyclic group is cycloalkyl, cycloheteroalkyl, aryl, or heteroaryl; and wherein said cyclic group is optionally substituted by one or more substituents J; each substituent J is independently selected from the group consisting of R', CN, CF3, C(O)OR', C(O)R', C(O)NR'2, NR'2, NO2, OR', SR', SO2, SOR', or SO3R', and additionally, or alternatively, two J groups on adjacent ring atoms form a fused 5- or 6-membered aromatic group; each R' is independently selected from halo, H, alkyl, alkenyl, alkynyl, heteroalkyl, aralkyl, aryl, and heteroaryl;
(X-Y) is selected from a photoactive ligand or an ancillary ligand, a is 0, 1, 2, 3, or 4; b is 0, 1, 2, or 3; m is a value from 1 to the maximum number of ligands that may be attached to metal M; m + n is the maximum number of ligands that may be attached to metal M.
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US10/880,384 US7393599B2 (en) 2004-05-18 2004-06-28 Luminescent compounds with carbene ligands
US11/032,885 US7534505B2 (en) 2004-05-18 2005-01-10 Organometallic compounds for use in electroluminescent devices
US11/031,078 2005-01-10
US11/032,836 2005-01-10
US11/032,941 US7582365B2 (en) 2005-01-10 2005-01-10 Reversibly reducible metal complexes as electron transporting materials for OLEDs
US11/032,887 US7601436B2 (en) 2004-05-18 2005-01-10 Carbene metal complexes as OLED materials
US11/032,950 US7279704B2 (en) 2004-05-18 2005-01-10 Complexes with tridentate ligands
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US11/030,901 US7655322B2 (en) 2004-05-18 2005-01-10 OLEDs utilizing macrocyclic ligand systems
US11/032,885 2005-01-10
US11/032,739 2005-01-10
US11/032,887 2005-01-10
US11/032,941 2005-01-10
US11/032,721 US7445855B2 (en) 2004-05-18 2005-01-10 Cationic metal-carbene complexes
US11/032,836 US7154114B2 (en) 2004-05-18 2005-01-10 Cyclometallated iridium carbene complexes for use as hosts
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