US20170250354A1 - Organic electroluminescent materials and devices - Google Patents

Organic electroluminescent materials and devices Download PDF

Info

Publication number
US20170250354A1
US20170250354A1 US15/594,046 US201715594046A US2017250354A1 US 20170250354 A1 US20170250354 A1 US 20170250354A1 US 201715594046 A US201715594046 A US 201715594046A US 2017250354 A1 US2017250354 A1 US 2017250354A1
Authority
US
United States
Prior art keywords
group
compound
independently selected
bzm
cycloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US15/594,046
Inventor
Chuanjun Xia
Jui-Yi Tsai
Beatriz Eguillor Armendáriz
Miguel A. Esteruelas Rodrigo
Roberto Gómez Alabau
Montserrat Oliván Esco
Enrique Oñate Rodriguez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universal Display Corp
Original Assignee
Universal Display Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universal Display Corp filed Critical Universal Display Corp
Priority to US15/594,046 priority Critical patent/US20170250354A1/en
Assigned to UNIVERSAL DISPLAY CORPORATION reassignment UNIVERSAL DISPLAY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ALABAU, ROBERTO GOMEZ, ARMENDARIZ, BEATRIZ EGUILLOR, ESCO, MONTSERRAT OLIVAN, RODRIGO, MIGUEL A. ESTERUELAS, RODRIGUEZ, ENRIQUE ONATE, TSAI, JUI-YI, XIA, CHUANJUN
Publication of US20170250354A1 publication Critical patent/US20170250354A1/en
Priority to US16/784,609 priority patent/US10930866B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • H01L51/0088—
    • 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 Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/002—Osmium compounds
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • H01L51/0054—
    • H01L51/0058—
    • H01L51/0067—
    • H01L51/0072—
    • H01L51/0074—
    • 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
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • 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
    • H10K85/348—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising osmium
    • 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
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • 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
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • 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
    • H01L51/5016—
    • 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

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: Regents of the University of Michigan, Princeton University, University of Southern California, and the 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 compounds for use as emitters and devices, such as organic light emitting diodes, including the same. More particularly, the compounds disclosed herein are novel heteroleptic bistridentate osmium carbene complexes and a novel synthetic method to make both homoleptic and heteroleptic bistridentate osmium carbene complexes.
  • 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.
  • 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. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
  • phosphorescent emissive molecules is a full color display.
  • Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors.
  • these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.
  • a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy) 3 , which has the following structure:
  • organic includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic 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.
  • top means furthest away from the substrate, while “bottom” means closest to the substrate.
  • 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 contact with” the second layer.
  • 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 ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material.
  • a ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
  • 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.
  • a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
  • L 1 -Os-L 2 wherein L 1 and L 2 are independently a biscarbene tridentate ligand, wherein L 1 and L 2 can be same or different is disclosed.
  • the method comprises: (a) reacting a precursor of ligand L 1 with an osmium precursor to form an intermediate product, wherein the osmium precursor having the formula OsH x (PR 3 ) y , wherein x is an integer from 2 to 6 and y is an integer from 2 to 5, and R is selected from the group consisting of aryl, alkyl and cycloalkyl; and (b) reacting a precursor of ligand L 2 with said intermediate product.
  • L 1 and L 2 are monoanionic ligands. In some embodiments, L 1 and L 2 are independently selected from ligands having Formula II:
  • Y 1 , Y 2 and Y 3 comprise C or N; wherein R 3 and R 4 may represent mono-, or di-substitutions, or no substitution; wherein R 5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents of R 1 , R 2 , R 3 , R
  • a first device comprising a first organic light emitting device.
  • the first organic light emitting device comprises an anode; a cathode; and an organic layer, disposed between the anode and the cathode.
  • the organic layer can comprise a compound having the structure according Formula I
  • novel compounds, heteroleptic bistridentate osmium carbene complexes, and a novel synthetic method to make both homoleptic and heteroleptic bistridentate osmium carbene complexes disclosed herein are useful as emitters in organic light emitting devices.
  • the inventors have discovered that the incorporation of these ligands can narrow the emission spectrum and improve device efficiency.
  • FIG. 1 shows an organic light emitting device
  • FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.
  • FIG. 3 shows molecular diagram of complex monohydride with X-ray diffraction analysis characterization.
  • FIG. 4 shows molecular diagram of Complex A with X-ray diffraction analysis characterization.
  • 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. Pat. 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.
  • FIG. 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 , a cathode 160 , and a barrier layer 170 .
  • 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. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.
  • each of these layers are available.
  • a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety.
  • 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 U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety.
  • Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety.
  • An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety.
  • the theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No.
  • FIG. 2 shows an inverted OLED 200 .
  • the device includes a substrate 210 , a 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 .
  • FIG. 2 provides one example of how some layers may be omitted from the structure of device 100 .
  • FIGS. 1 and 2 The simple layered structure illustrated in FIGS. 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.
  • 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 FIGS. 1 and 2 .
  • OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to 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. Pat. 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 FIGS. 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. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.
  • 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. Pat. 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. Pat. 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. Pat. No. 7,431,968, which is incorporated by reference in its entirety.
  • OVPD organic vapor phase deposition
  • 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. Pat. 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.
  • Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer.
  • a barrier layer One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc.
  • the barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge.
  • the barrier layer may comprise a single layer, or multiple layers.
  • the barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer.
  • the barrier layer may incorporate an inorganic or an organic compound or both.
  • the preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties.
  • the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time.
  • the weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95.
  • the polymeric material and the non-polymeric material may be created from the same precursor material.
  • the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
  • 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, medical 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, 3-D 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. 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.), but could be used outside this temperature range, for example, from ⁇ 40 degree C. to +80 degree C.
  • 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.
  • halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference.
  • substituted indicates that a substituent other than H is bonded to the relevant carbon.
  • R 2 is monosubstituted, then one R 2 must be other than H.
  • R 3 is disubstituted, then two of R 3 must be other than H.
  • R 2 is unsubstituted R 2 is hydrogen for all available positions.
  • novel heteroleptic bistridentate Os(II) complexes and a novel method for synthesizing both homoleptic and heteroleptic bistridentate Os(II) complexes is provided.
  • Heteroleptic osmium complexes provide great freedom of tuning emission color, electrochemical energy levels, and improving evaporation properties.
  • Osmium (II) complexes have been investigated for OLED applications.
  • the octahedral ligand arrangement of the Os(II) complexes resembles that of Ir(III) complexes.
  • Os(II) complexes generally exhibit low oxidation potential, i.e. shallow HOMO energy level than Ir(III) complexes.
  • bistridentate Os(II) carbene complexes offer performance advantages for OLED applications. Without being bound to a theory, the inventors believe that the rigid nature of the tridentate ligands are providing narrow emission line widths and short excited state lifetimes, which can result in better color purity and longer device lifetime, making them suitable for display applications.
  • the inventors have developed a new stepwise complexation method. This method is suitable for making both homoleptic and heteroleptic bistridentate Os(II) complexes.
  • This method is suitable for making both homoleptic and heteroleptic bistridentate Os(II) complexes.
  • an osmium precursor was first reacted with a bistridentate ligand to generate an intermediate that has one tridentate ligand coordinated to the metal.
  • the intermediate was then treated with another tridentate ligand to generate the final complex.
  • homoleptic or heteroleptic complexes can be synthesized. In addition, the yield was improved.
  • One example of the inventive synthetic method is shown below:
  • Coupling constants J and N are given in hertz. Attenuated total reflection infrared spectra (ATR-IR) of solid samples were run on a Perkin-Elmer Spectrum 100 FT-IR spectrometer. C, H, and N analyses were carried out in a Perkin-Elmer 2400 CHNS/O analyzer. High-resolution electrospray mass spectra were acquired using a MicroTOF-Q hybrid quadrupole time-of-flight spectrometer (Bruker Daltonics, Bremen, Germany). OsH 6 (P i Pr 3 ) 2 was prepared by the method published in Aracama, M.; Esteruelas, M. A.; Lahoz, F. J.; López, J. A.; Meyer, U.; Oro, L. A.; Werner, H. Inorg. Chem. 1991, 30, 288.
  • This monohydride compound can be prepared by using two different methods.
  • THF tetrahydrofuran
  • FIG. 3 shows the molecular structure of complex monohydride with the X-ray diffraction analysis characterization.
  • FIG. 4 shows molecular diagram of Complex A with X-ray diffraction analysis characterization.
  • the structure has two chemically equivalent but crystallographically independent molecules in the asymmetric unit.
  • L 1 -Os-L 2 wherein L 1 and L 2 are independently a biscarbene tridentate ligand, wherein L 1 and L 2 can be same or different is disclosed.
  • the method comprises: (a) reacting a precursor of ligand L 1 with an osmium precursor to form an intermediate product, wherein the osmium precursor having the formula OsH x (PR 3 ) y , wherein x is an integer from 2 to 6 and y is an integer from 2 to 5, and R is selected from the group consisting of aryl, alkyl and cycloalkyl; and (b) reacting a precursor of ligand L 2 with said intermediate product.
  • L 1 and L 2 are monoanionic ligands. In some embodiments, L 1 and L 2 are independently selected from ligands having Formula II:
  • Y 1 , Y 2 and Y 3 comprise C or N; wherein R 3 and R 4 may represent mono-, or di-substitutions, or no substitution; wherein R 5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents of R 1 , R 2 , R 3 , R
  • Y 1 , Y 2 and Y 3 comprise C. In one embodiment, Y 1 and Y 3 comprise C, and Y 2 is N. In one embodiment, Y 1 and Y 3 are N, and Y 2 comprise C. In one embodiment, R 1 and R 2 are independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and partially or fully deuterated variants thereof.
  • R 1 and R 2 are independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.
  • the osmium precursor having the formula OsH 6 (PR 3 ) 2 is selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, and 2-methylphenyl.
  • R is 1-methylethyl.
  • the ligands having Formula II are selected from the group consisting of:
  • a compound having a structure according to Formula I, L 1 -Os-L 2 is provided, wherein L 1 and L 2 are different; wherein L 1 and L 2 are independently selected from ligands having Formula II,
  • Y 1 , Y 2 and Y 3 comprise C or N; wherein R 3 and R 4 may represent mono-, or di-substitutions, or no substitution; wherein R 5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R 1 and R 2 are independently selected from the group consisting of alkyl and cycloalkyl; wherein R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof; wherein any two adjacent substituents of R 1 , R 2 , R 3 , R 4 and R 5 are optionally joined to condense into a fused ring; and wherein the dash lines show the connection points to osmium.
  • Y 1 , Y 2 and Y 3 comprise C. In one embodiment of the compound, Y 1 and Y 3 comprise C, and Y 2 is N. In some embodiments, Y 1 and Y 3 are N, and Y 2 comprise C. In one embodiment, R 1 and R 2 are independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and partially or fully deuterated variants thereof.
  • R 1 and R 2 are independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.
  • L 1 and L 2 are independently selected from ligands having Formula III:
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 comprise C or N.
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 comprise C.
  • the ligands having Formula II are selected from the group consisting of: L 101 to L 159 defined herein.
  • the compound having a structure according to Formula I, L 1 -Os-L 2 is selected from the group consisting of Compounds 1 to 1159 defined in Table 1 below:
  • L 101 L 102 1.
  • L 101 L 103 3.
  • L 101 L 104 4.
  • L 101 L 105 5.
  • L 101 L 106 6.
  • L 101 L 107 7.
  • L 101 L 108 8.
  • L 101 L 109 9.
  • L 101 L 110 10.
  • L 101 L 111 11.
  • L 101 L 112 12.
  • L 101 L 113 13.
  • L 101 L 114 14.
  • L 101 L 115 15.
  • L 101 L 116 16 L 101 L 117 17.
  • L 101 L 118 18.
  • L 101 L 119 19.
  • L 101 L 120 20.
  • L 101 L 121 21.
  • L 101 L 125 25.
  • L 101 L 126 26.
  • L 101 L 127 27.
  • L 101 L 129 29 19.
  • L 101 L 130 30.
  • L 101 L 140 40.
  • L 101 L 150 50.
  • L 103 L 110 123.
  • L 103 L 111 124.
  • L 103 L 112 125.
  • L 103 L 113 126.
  • L 103 L 114 127.
  • L 103 L 116 129.
  • L 103 L 118 131.
  • L 103 L 119 132.
  • L 103 L 120 133.
  • L 103 L 125 138.
  • L 103 L 128 141.
  • L 103 L 130 143 143.
  • L 105 L 110 232.
  • L 108 L 110 388. L 108 L 111 389. L 108 L 112 390. L 108 L 113 391. L 108 L 114 392. L 108 L 115 393. L 108 L 116 394. L 108 L 117 395. L 108 L 118 396. L 108 L 119 397. L 108 L 120 398. L 108 L 121 399. L 108 L 122 400. L 108 L 123 401. L 108 L 124 402. L 108 L 125 403. L 108 L 126 404. L 108 L 127 405. L 108 L 128 406. L 108 L 129 407. L 108 L 130 408. L 108 L 131 409.
  • L 122 L 140 1027.
  • L 122 L 150 1037.
  • L 122 L 152 1039.
  • L 125 L 140 1132. L 125 L 141 1133. L 125 L 142 1134. L 125 L 143 1135. L 125 L 144 1136. L 125 L 145 1137. L 125 L 146 1138. L 125 L 147 1139. L 125 L 148 1140. L 125 L 149 1141. L 125 L 150 1142. L 125 L 151 1143. L 125 L 152 1144. L 125 L 153 1145. L 125 L 154 1146. L 125 L 155 1147. L 125 L 156 1148. L 125 L 157 1149. L 125 L 158 1150. L 125 L 159
  • a first device comprising a first organic light emitting device.
  • the first organic light emitting device comprises an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound having the structure according Formula I, L 1 -Os-L 2 ; wherein L 1 and L 2 are different; wherein L 1 and L 2 are independently selected from ligands having Formula II:
  • Y 1 , Y 2 and Y 3 comprise C or N; wherein R 3 and R 4 may represent mono-, or di-substitutions, or no substitution; wherein R 5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R 1 and R 2 are independently selected from the group consisting of alkyl and cycloalkyl; wherein R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof; wherein any two adjacent substituents of R 1 , R 2 , R 3 , R 4 and R 5 are optionally joined to condense into a fused ring; and wherein the dash lines show the connection points to osmium.
  • Y 1 , Y 2 and Y 3 comprise C. In one embodiment, Y 1 , Y 2 and Y 3 are N. In one embodiment, R 1 and R 2 are independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.
  • L 1 and L 2 are independently selected from ligands having Formula III:
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 comprise C or N.
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 comprise C.
  • the ligands having Formula II are selected from the group consisting of L 101 to L 159 defined herein.
  • the first emitting compound is selected from the group consisting of Compounds 1 to 1159 defined in Table 1.
  • the first device can be one or more of a consumer product, an organic light-emitting device, and/or a lighting panel.
  • the organic layer in the organic light emitting device can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
  • the organic layer can also include a host.
  • the host can include a metal complex.
  • the host can be a metal 8-hydroxyquinolate.
  • the host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan.
  • Any substituent in the host can be an unfused substituent independently selected from the group consisting of C n H 2n+1 , OC n H 2n+1 , OAr 1 , N(C n H 2n+1 ) 2 , N(Ar 1 )(Ar 2 ), CH ⁇ CH—C n H 2n+1 , C ⁇ C—C n H 2n+1 , Ar 1 , Ar 1 —Ar 2 , C n H 2n —Ar 1 , or no substitution.
  • n can range from 1 to 10; and Ar 1 and Ar 2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
  • the host can be a compound selected from the group consisting of carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
  • the “aza” designation in the fragments described above, i.e., aza-dibenzofuran, aza-dibenzonethiophene, etc. means that one or more of the C—H groups in the respective fragment can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline.
  • azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline.
  • the host can include a metal complex.
  • the host can be a specific compound selected from the group consisting of:
  • a formulation comprising the compound having a structure according to Formula I, L 1 -Os-L 2 , as defined herein, is disclosed.
  • the formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, and an electron transport layer material, disclosed herein.
  • the materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device.
  • emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present.
  • the materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
  • a hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material.
  • the material include, but not limit to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO x ; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
  • aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
  • Each of Ar 1 to Ar 9 is selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrim
  • each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
  • a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acy
  • Ar 1 to Ar 9 is independently selected from the group consisting of:
  • k is an integer from 1 to 20;
  • X 101 to X 108 is C (including CH) or N;
  • Z 101 is NAr 1 , O, or S;
  • Ar 1 has the same group defined above.
  • metal complexes used in HIL or HTL include, but not limit to the following general formula:
  • Met is a metal, which can have an atomic weight greater than 40;
  • (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 are independently selected from C, N, O, P, and S;
  • L 101 is an ancillary ligand;
  • k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and
  • k′+k′′ is the maximum number of ligands that may be attached to the metal.
  • (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. In another aspect, (Y 101 -Y 102 ) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc + /Fc couple less than about 0.6 V.
  • the light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material.
  • the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.
  • metal complexes used as host are preferred to have the following general formula:
  • Met is a metal
  • (Y 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104 are independently selected from C, N, O, P, and S
  • L 11 is an another ligand
  • k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal
  • k′+k′′ is the maximum number of ligands that may be attached to the metal.
  • the metal complexes are:
  • (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
  • Met is selected from Ir and Pt.
  • (Y 103 -Y 104 ) is a carbene ligand.
  • organic compounds used as host are selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine
  • each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
  • a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acy
  • host compound contains at least one of the following groups in the molecule:
  • R 101 to R 107 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above k is an integer from 0 to 20 or 1 to 20; k′′′ is an integer from 0 to 20.
  • X 101 to X 108 is selected from C (including CH) or N.
  • Z 101 and Z 102 is selected from NR 101 , O, or S.
  • a hole blocking layer may be used to reduce the number of holes and/or excitons that leave the emissive layer.
  • 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.
  • compound used in HBL contains the same molecule or the same functional groups used as host described above.
  • compound used in HBL contains at least one of the following groups in the molecule:
  • Electron transport layer may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
  • compound used in ETL contains at least one of the following groups in the molecule:
  • R 101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above.
  • Ar 1 to Ar 3 has the similar definition as Ar's mentioned above.
  • k is an integer from 1 to 20.
  • X 101 to X 108 is selected from C (including CH) or N.
  • the metal complexes used in ETL contains, but not limit to the following general formula:
  • (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L 101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
  • the hydrogen atoms can be partially or fully deuterated.
  • any specifically listed substituent such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof.
  • classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.
  • hole injection materials In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exciton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED.
  • Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table 2 below. Table 2 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.
  • Metal 8-hydroxyquinolates e.g., BAlq
  • Appl. Phys. Lett. 81, 162 (2002) 5-member ring electron deficient heterocycles such as triazole, oxadiazole, imidazole, benzoimidazole Appl. Phys. Lett. 81, 162 (2002) Triphenylene compounds US20050025993 Fluorinated aromatic compounds Appl. Phys. Lett.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

A method of making an osmium(II) complex having Formula I, L1-Os-L2, wherein L1 and L2 are independently a biscarbene tridentate ligand, wherein L1 and L2 can be same or different is disclosed. The method includes (a) reacting a precursor of ligand L1 with an osmium precursor to form an intermediate product, wherein the osmium precursor having the formula OsHx(PR3)y, wherein x is an integer from 2 to 6 and y is an integer from 2 to 5, and R is selected from the group consisting of aryl, alkyl and cycloalkyl; and (b) reacting a precursor of ligand L2 with said intermediate product.

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • This application is a continuation of U.S. application Ser. No. 13/950,591, filed Jul. 25, 2013, the entirety of which is incorporated herein by reference.
    • PARTIES TO A JOINT RESEARCH AGREEMENT
  • 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: Regents of the University of Michigan, Princeton University, University of Southern California, and the 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
  • The present invention relates to compounds for use as emitters and devices, such as organic light emitting diodes, including the same. More particularly, the compounds disclosed herein are novel heteroleptic bistridentate osmium carbene complexes and a novel synthetic method to make both homoleptic and heteroleptic bistridentate osmium carbene complexes.
    • BACKGROUND
  • 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 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. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
  • One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.
  • One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)3, which has the following structure:
  • Figure US20170250354A1-20170831-C00001
  • In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.
  • As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic 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.
  • As used herein, “top” means furthest away from the substrate, while “bottom” means closest to 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 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.
  • 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.
  • A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
  • 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.
  • As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
  • More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
    • SUMMARY OF THE INVENTION
  • According to an aspect of the present disclosure, a method of making an osmium(II) complex having Formula I
  • L1-Os-L2, wherein L1 and L2 are independently a biscarbene tridentate ligand, wherein L1 and L2 can be same or different is disclosed. The method comprises: (a) reacting a precursor of ligand L1 with an osmium precursor to form an intermediate product, wherein the osmium precursor having the formula OsHx(PR3)y, wherein x is an integer from 2 to 6 and y is an integer from 2 to 5, and R is selected from the group consisting of aryl, alkyl and cycloalkyl; and (b) reacting a precursor of ligand L2 with said intermediate product.
  • In one embodiment of the method, L1 and L2 are monoanionic ligands. In some embodiments, L1 and L2 are independently selected from ligands having Formula II:
  • Figure US20170250354A1-20170831-C00002
  • wherein Y1, Y2 and Y3 comprise C or N; wherein R3 and R4 may represent mono-, or di-substitutions, or no substitution; wherein R5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R1, R2, R3, R4 and R5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents of R1, R2, R3, R4 and R5 are optionally joined to form a ring; and wherein the dash lines show the connection points to osmium.
  • According to an embodiment, a compound having the structure according to Formula I as defined herein is disclosed.
  • According to another aspect of the present disclosure, a first device comprising a first organic light emitting device is disclosed. The first organic light emitting device comprises an anode; a cathode; and an organic layer, disposed between the anode and the cathode. The organic layer can comprise a compound having the structure according Formula I
  • The novel compounds, heteroleptic bistridentate osmium carbene complexes, and a novel synthetic method to make both homoleptic and heteroleptic bistridentate osmium carbene complexes disclosed herein are useful as emitters in organic light emitting devices. The inventors have discovered that the incorporation of these ligands can narrow the emission spectrum and improve device efficiency.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 shows an organic light emitting device.
  • FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.
  • FIG. 3 shows molecular diagram of complex monohydride with X-ray diffraction analysis characterization.
  • FIG. 4 shows molecular diagram of Complex A with X-ray diffraction analysis characterization.
    •  DETAILED DESCRIPTION
  • 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.
  • The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. 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.
  • 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 is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
  • FIG. 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, a cathode 160, and a barrier layer 170. 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. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.
  • More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. 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 U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, 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 theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
  • FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a 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. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.
  • The simple layered structure illustrated in FIGS. 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 FIGS. 1 and 2.
  • 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 to 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. Pat. 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 FIGS. 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. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.
  • 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. Pat. 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. Pat. 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. Pat. No. 7,431,968, 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. Pat. 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.
  • Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
  • 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, medical 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, 3-D 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.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.
  • 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.
  • The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference.
  • As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant carbon. Thus, where R2 is monosubstituted, then one R2 must be other than H. Similarly, where R3 is disubstituted, then two of R3 must be other than H. Similarly, where R2 is unsubstituted R2 is hydrogen for all available positions.
  • In the present disclosure, novel heteroleptic bistridentate Os(II) complexes and a novel method for synthesizing both homoleptic and heteroleptic bistridentate Os(II) complexes is provided. Heteroleptic osmium complexes provide great freedom of tuning emission color, electrochemical energy levels, and improving evaporation properties.
  • Osmium (II) complexes have been investigated for OLED applications. The octahedral ligand arrangement of the Os(II) complexes resembles that of Ir(III) complexes. Os(II) complexes generally exhibit low oxidation potential, i.e. shallow HOMO energy level than Ir(III) complexes. The inventors have discovered that bistridentate Os(II) carbene complexes offer performance advantages for OLED applications. Without being bound to a theory, the inventors believe that the rigid nature of the tridentate ligands are providing narrow emission line widths and short excited state lifetimes, which can result in better color purity and longer device lifetime, making them suitable for display applications.
  • US2005260449 and WO2009046266 disclosed bistridentate Os(II) complexes. Examples of homoleptic Os(II) complexes were provided. The two tridentate ligands binding to Os(II) metal are identical. It may be beneficial to incorporate two different ligands to Os(II) metal to form a heterlopetic complex. For example, the thermal properties, electrochemical properties, and photophysical properties can be tuned by selecting two proper ligands. It offers more flexibility for materials design than two identical ligands.
  • The synthesis of homoleptic complexes, however, has been challenging; let alone the heteroleptic complexes. The synthesis method used in WO2009046266 generated very low yield, typically 2-5%. In a later application, US2012215000, the yield was significantly improved to over 30% using a new osmium precursor. In theory, both of these methods should work for synthesis of heteroleptic bistridentate Os(II) complexes by introducing two different ligands at the complexation stage and isolating the desired heteroleptic complex from the reaction mixture. The synthesis will be extremely inefficient and impractical.
  • The inventors have developed a new stepwise complexation method. This method is suitable for making both homoleptic and heteroleptic bistridentate Os(II) complexes. As shown in the scheme below, an osmium precursor was first reacted with a bistridentate ligand to generate an intermediate that has one tridentate ligand coordinated to the metal. The intermediate was then treated with another tridentate ligand to generate the final complex. Depending on the structure of the second ligand, homoleptic or heteroleptic complexes can be synthesized. In addition, the yield was improved. One example of the inventive synthetic method is shown below:
  • Figure US20170250354A1-20170831-C00003
  • In describing the novel synthesis method of the inventors, all reactions were carried out with rigorous exclusion of air using Schlenk-tube techniques. Solvents, except DMF and acetonitrile that were dried and distilled under argon, were obtained oxygen- and water-free from an MBraun solvent purification apparatus. 1H 31P{1H}, 19F and 13C{1H} NMR spectra were recorded on Bruker 300 ARX, Bruker Avance 300 MHz, and Bruker Avance 400 MHz instruments. Chemical shifts (expressed in parts per million) are referenced to residual solvent peaks (1H, 13C{1H}) or external 85% H3PO4 (31P{1H}), or external CFCl3 (19F). Coupling constants J and N are given in hertz. Attenuated total reflection infrared spectra (ATR-IR) of solid samples were run on a Perkin-Elmer Spectrum 100 FT-IR spectrometer. C, H, and N analyses were carried out in a Perkin-Elmer 2400 CHNS/O analyzer. High-resolution electrospray mass spectra were acquired using a MicroTOF-Q hybrid quadrupole time-of-flight spectrometer (Bruker Daltonics, Bremen, Germany). OsH6(PiPr3)2 was prepared by the method published in Aracama, M.; Esteruelas, M. A.; Lahoz, F. J.; López, J. A.; Meyer, U.; Oro, L. A.; Werner, H. Inorg. Chem. 1991, 30, 288.
  • Preparation of Dihydride-BF4
  • Figure US20170250354A1-20170831-C00004
  • A solution of OsH6(PiPr3)2 (261 mg, 0.505 mmol) in dimethylformamide (DMF) (5 mL) was treated with 1,3-bis[(1-methyl)benzylimidazolium-3-yl]benzene diiodide (300 mg, 0.505 mmol). The resulting mixture was refluxed for 20 min, getting a very dark solution. After cooling at room temperature the solvent was removed in vacuo, affording a dark residue. The residue was dissolved in acetonitrile (10 mL) and AgBF4 (98.3 mg, 0.505 mmol) was added. After stirring protected from the light for 30 min the resulting suspension was filtered through Celite to remove the silver salts. The solution thus obtained was evaporated to ca. 0.5 mL and diethyl ether (10 mL) was added to afford a beige solid, that was washed with further portions of diethyl ether (2×2 mL) and dried in vacuo. Yield: 240 mg (50%). Analytical Calculation for C40H61BF4N4OsP2: C, 51.28; H, 6.56; N, 5.98. Found: C, 51.55; H, 6.70; N, 5.62. HRMS (electrospray, m/z): calcd for C40H61N4OsP2 [M]+: 851.3983; found: 851.4036. IR (cm−1): ν(Os—H) 2104 (w), ν(BF4) 1080-1000 (vs). 1H NMR (300 MHz, CD3CN, 298K): δ 8.31 (m, 2H, CH bzm), 7.98 (d, JH—H=7.9, 2H, CH Ph), 7.70 (m, 2H, CH bzm), 7.57 (t, JH—H=7.9, 1H, CH Ph), 7.54-7.50 (m, 4H, CH bzm), 4.32 (s, 6H, CH3), 1.54 (m, 6H, PCH(CH3)2), 0.67 (dvt, JHH=6.2, N=13.2, 36H, PCH(CH3)2), −6.25 (t, JH—P=13.6, 2H, Os—H). 13C{1H} NMR (75.42 MHz, CD3CN, 293K): δ 189.4 (t, JC—P=7.5, NCN), 161.3 (Os—C), 146.9 (s, C Ph), 137.3 (s, C Bzm), 132.8 (s, C Bzm), 124.9 (s, CH Bzm), 124.5 (s, CH Bzm), 124.2 (s, CH Ph), 112.8 (s, CH Bzm), 111.9 (s, CH Bzm), 109.2 (s, CH Ph), 38.9 (s, CH3), 29.3 (t, N=27, PCH(CH3)2), 18.5 (s, PCH(CH3)2). 31P{1H} NMR (121.4 MHz, CD3CN, 293K): δ 4.5 (s).
  • Preparation of complex monohydride, shown below:
  • Figure US20170250354A1-20170831-C00005
  • This monohydride compound can be prepared by using two different methods. Method (A): A solution of OsH6(PiPr3)2 (261 mg, 0.505 mmol) in DMF (5 mL) was treated with 1,3-bis[(1-methyl)benzylimidazolium-3-yl]benzene diiodide (300 mg, 0.505 mmol). The resulting mixture was refluxed for 20 min, getting a very dark solution. After cooling at room temperature the solvent was removed in vacuo, affording a dark residue. The dark residue was dissolved in 10 mL of tetrahydrofuran (THF) and KtBuO (142 mg, 1.263 mmol) was added to the solution. After stirring at room temperature for 10 min the resulting suspension was filtered through Celite to remove the potassium salts. The solution thus obtained was evaporated to dryness to afford a yellow residue. Addition of pentane afforded a yellow solid, which was washed with pentane (1×2 mL) and dried in vacuo to obtain a yellow solid. Yield: 378 mg (88%). Method (B): A solution of dihydride-BF4 (200 mg, 0.213 mmol) in THF (5 mL) was treated with KtBuO (28.6 mg, 0.255 mmol). After stirring at room temperature for 10 min the resulting suspension was filtered through Celite to remove the potassium salts. The solution thus obtained was evaporated to dryness to afford a yellow residue. Addition of pentane afforded a yellow solid, which was washed with pentane (1×2 mL) and dried in vacuo obtain a yellow solid. Yield: 163 mg (90%). Anal. Calcd. for C40H60N4OsP2: C, 56.58; H, 7.12; N, 6.60. Found: C, 56.00; H, 6.69; N, 6.76. HRMS (electrospray, m/z): calcd. For [M+H]+ 851.3983; found: 851.3979. IR (cm−1): ν(Os—H) 1889 (w). 1H NMR (300 MHz, C6D6, 298K): δ 8.17 (d, JH—H=7.7, 2H, CH Ph), 8.06 (d, JH—H=7.7, 2H, CH bzm), 7.60 (t, JH—H=7.7, 1H, CH Ph), 7.20 (td, JH—H=7.9, JH—H=1.0, 2H, CH bzm), 7.14-7.03 (m, 4H CH bzm), 3.92 (s, 6H, CH3), 1.55 (m, 6H, PCH(CH3)2), 0.67 (dvt, JH.H=6.9, N=12.3, 36H, PCH(CH3)2), −9.55 (t, JH—P=33.6, 1H, Os—H). 13C{1H} NMR (75.42 MHz, C6D6, 293K): δ 197.6 (t, JC—P=9.2, Os—NCN), 173.2 (t, JC—P=2.9, Os—C), 148.4 (s, C Ph), 137.3 (s, C Bzm), 134.4 (s, C Bzm), 121.5 (s, CH Bzm), 121.2 (s, CH Bzm), 117.9 (s, CH Ph), 109.6 (s, CH Bzm), 108.5 (s, CH Bzm), 105.8 (s, CH Ph), 37.9 (s, CH3), 31.0 (t, N=24.2, PCH(CH3)2), 19.7 (s, PCH(CH3)2). 31P{1H} NMR (121.4 MHz, C6D6, 293K): δ 20.6 (s, doublet under off resonance conditions). FIG. 3 shows the molecular structure of complex monohydride with the X-ray diffraction analysis characterization. Selected bond lengths (Å) and angles (°) were: Os—P(1)=2.3512(18), Os—P(2)=2.3529(17), Os—C(1)=2.052(6), Os—C(9)=2.036(3), Os—C(15)=2.035(6); P(1)-Os—P(2)=152.86(6), C(1)-Os—C(9)=75.5(2), C(9)-Os—C(15)=75.4(2), C(1)-Os(C15)=150.9(2).
  • Preparation of Complex Monohydride-CF3:
  • Figure US20170250354A1-20170831-C00006
    • Method (A):
  • A solution of dihydride-CF3-BF4 (200 mg, 0.2 mmol) in THF (5 mL) was treated with KtBuO (26.8 mg, 0.24 mmol). After stirring at room temperature for 10 min the resulting suspension was filtered through Celite to remove the potassium salts. The solution thus obtained was evaporated to dryness to afford a yellow residue. Addition of pentane afforded a yellow solid, which was washed with pentane (1×2 mL) and dried in vacuo obtain a yellow solid. Yield: 240 mg (50%). Anal. Calcd. for C41H59F3N4OsP2: C, 53.69; H, 6.48; N, 6.11. Found: C, 53.20; H, 6.33; N, 6.18. IR (cm−1): ν(Os—H) 1842 (w). 1H NMR (300 MHz, C6D6, 298K): δ 8.53 (s, 2H, CH Ph-CF3), 8.18 (m, 2H, CH bzm), 7.15-6.98 (m, 6H, CH bzm), 3.86 (s, 6H, CH3), 1.49 (m, 6H, PCH(CH3)2), 0.60 (dvt, JH.H=6.6, N=12.9, 36H, PCH(CH3)2), −9.29 (t, JH—P=34.0, 1H, Os—H). 13C{1H} NMR (75.42 MHz, C6D6, 293K): δ 197.4 (t, JC—P=9.0, Os—NCN), 173.2 (t, JC—P=3.6, Os—C), 148.0 (s, C Ph), 137.2 (s, C Bzm), 133.9 (s, C Bzm), 128.2 (q, JC—F=270.0, CF3), 122.0 (s, CH Bzm), 121.7 (s, CH Bzm), 118.9 (q, JC—F=30.8, C—CF3), 109.8 (s, CH Bzm), 108.7 (s, CH Bzm), 102.0 (q, JC—F=4.0 CH Ph), 37.9 (s, CH3), 30.9 (t, N=24.8, PCH(CH3)2), 19.5 (s, PCH(CH3)2). 31P{1H} NMR (121.4 MHz, C6D6, 293K): δ 21.4 (s, doublet under off resonance conditions). 19F NMR 282 MHz, C6D6, 293K): δ −60.10 (CF3). Method (B): A solution of OsH6(PiPr3)2 (235 mg, 0.455 mmol) in DMF (5 mL) was treated with 1,3-bis[(1-methyl)benzylimidazolium-3-yl]-5-trifluoromethyl-benzene diiodide (300 mg, 0.455 mmol). The resulting mixture was refluxed for 20 min, getting a very dark solution. After cooling at room temperature the solvent was removed in vacuo, affording a dark residue. The addition of 4 mL of toluene caused the precipitation of a brown solid that was washed with further portions of diethyl ether (2×4 mL). The brown solid was dissolved in THF (10 mL) and KtBuO (102 mg, 0.906 mmol) was added. After stirring for 20 min the resulting suspension was filtered through Celite to remove the iodide salts. The solution thus obtained was evaporated to dryness and pentane (4 mL) was added to afford an orange solid that was washed with further portions of pentane (1×3 mL) and dried in vacuo. This orange solid was suspended in diethyl ether (10 mL) and treated with HBF4:Et2O (93 μL, 0.680 mmol) getting a white suspension. This solid was decanted, washed with further portions of diethyl ether (2×4 mL) and dried in vacuo. Yield: 405 mg (89%) Anal. Calcd. for C41H60BF7N4OsP2: C, 49.00; H, 6.02; N, 5.58. Found: C, 49.21; H, 5.79; N, 5.69. HRMS (electrospray, m/z): calcd for [M]+: 919.3857; found: 919.4035. IR (cm−1): ν(Os—H) 2097 (w), ν(BF4) 1080-1000 (vs). 1H NMR (300 MHz, CD3CN, 298K): δ 9.60 (m, 2H, CH bzm), 9.41 (s, 2H, CH Ph), 8.96 (m, 2H, CH bzm), 8.80 (m, 4H, CH bzm), 5.57 (s, 6H, CH3), 2.80 (m, 6H, CHP), 1.91 (dvt, 36H, JHH=7.1, N=13.5, CH3-P), −4.70 (t, 2H, JH—P=13.5, Hhyd); 13C{1H} NMR (75.42 MHz, CD3CN, 293K): δ 189.6 (t, JC—P=7.5, NCN), 169.6 (t, JC—P=5.7, Os—C), 146.7 (s, C Ph), 137.4 (s, C Bzm), 132.6 (s, C Bzm), 126.7 (q, JC—F=270, CF3), 126.3 (q, JC—F=28.6, CCF3), 125.4 (s, CH Bzm), 125.1 (s, CH Bzm), 113.2 (s, CH Bzm), 112.3 (s, CH Bzm), 105.6 (q, JC—F=3.9, CH Ph), 39.1 (s, CH3), 29.5 (t, N=13.5, PCH(CH3)2), 19.6 (s, PCH(CH3)2). 31P{1H} NMR (121.4 MHz, CD3CN, 293K): δ 5.2 (s). 19F{1H} NMR (282 MHz, CD3CN, 293K): δ −60.21 (s, CF3); −151.7 (broad signal, BF4)
  • Preparation of Complex A:
  • Figure US20170250354A1-20170831-C00007
  • Monohydride (250 mg, 0.294 mmol) and 1,3-bis[(1-methyl)benzylimidazolium-3-yl]benzene ditetrafluoroborate (181 mg, 0.353 mmol) were dissolved in 5 mL of DMF and triethyl amine (0.6 mL, 4.4 mmol) was added to the solution. The resulting mixture was refluxed for 1.5 h and then it was cooled to room temperature. The solvent was evaporated under vacuum to afford a brown residue. Addition of acetonitrile afforded a bright yellow solid that was washed with acetonitrile (1×2 mL) and dried in vacuo. Yield: 153 mg (60%). HRMS (electrospray, m/z): calcd for C44H34N8Os [M]+: 867.2562; found: 867.2597. 1H NMR (300 MHz, C6D6, 293K): δ 8.29 (d, JH—H=7.7, 4H, CH Ph), 8.18 (d, JH—H=7.9, 4H, CH bzm), 7.81 (t, JH—H=7.7, 2H, CH Ph), 7.08 (td, JH—H=7.9, JH—H=1.0, 4H, CH bzm), 6.80 (td, JH—H=7.9, JH—H=1.0, 4H, CH bzm), 6.18 (d, JH—H=7.9, 4H, CH bzm), 2.25 (s, 12H, CH3). 13C{1H} NMR (75.42 MHz, C6D6, 293K): δ 192.6 (s, Os—NCN), 171.1 (s, Os—C), 146.8 (s, C Ph), 137.2 (s, C Bzm), 133.4 (s, C Bzm), 121.43 (s, CH Bzm), 121.03 (s, CH Bzm), 117.8 (s, CH Ph), 109.9 (s, CH Bzm), 109.0 (s, CH Bzm), 106.4 (s, CH Ph), 32.7 (s, CH3). FIG. 4 shows molecular diagram of Complex A with X-ray diffraction analysis characterization. The structure has two chemically equivalent but crystallographically independent molecules in the asymmetric unit. Selected bond lengths (Å) and angles (°): Os(1)-C(10)=2.048(7), 2.057(7), Os(1)-C(32)=2.045(7), 2.049(8), Os(1)-C(15)=2.026(8), 2.032(8), Os(1)-C(1)=2.042(8), 2.037(7), Os(1)-C(23)=2.049(7), 2.037(8), Os(1)-C(37)=2.043(7), 2.051(8); C(15)-Os(1)-C(1)=149.6(3), 149.9(3), C(23)-Os(1)-C(37)=150.0(3), 150.6(3), C(10)-Os(1)-C(32)=177.8(3), 178.6(3).
  • Preparation of Complex A-CF3:
  • Figure US20170250354A1-20170831-C00008
  • Monohydride (250 mg, 0.294 mmol) and 1,3-bis[(1-methyl)benzylimidazolium-3-yl]-5-trifluoromethyl-benzene ditetrafluoroborate (170 mg, 0.294 mmol) were dissolved in 5 mL of DMF and triethyl amine (0.6 mL, 4.4 mmol) was added to the solution. The resulting mixture was refluxed for 1.5 h and then it was cooled to room temperature. The solvent was evaporated under vacuum to afford a brown residue. Addition of acetonitrile afforded a bright yellow solid that was washed with acetonitrile (1×2 mL) and dried in vacuo. Yield: 147 mg (53%). HRMS (electrospray, m/z): calcd for C45H33F3N8Os [M]+: 934.2392; found: 934.2398. 1H NMR (300 MHz, C6D6, 293K): δ 8.75 (s, 2H, CH Ph-CF3), 8.24 (d, JH—H=7.8, 2H, CH Ph), 8.16 (d, JH—H=7.8, 2H, CH bzm), 8.14 (d, JH—H=7.8, 2H, CH bzm), 7.78 (t, JH—H=7.8, 1H, CH Ph), 7.08 (t, JH—H=7.8, 2H, CH bzm), 6.99 (t, JH—H=7.8, 2H, CH bzm), 6.81 (t, JH—H=7.9, 2H, CH bzm), 6.78 (t, JH—H=7.9, 2H, CH bzm), 6.21 (d, JH—H=7.8, 2H, CH bzm), 6.14 (d, JH—H=7.8, 2H, CH bzm), 2.22 (s, 6H, CH3), 2.11 (s, 6H, CH3). 13C{1H} NMR (100.63 MHz, C6D6, 293K): δ 192.4 (s, Os—NCN), 192.1 (s, Os—NCN), 179.0 (s, Os—C), 170.1 (s, Os—C), 146.7 (s, C Ph), 146.5 (s, C Ph), 137.2 (s, C Bzm), 137.1 (s, C Bzm), 133.4 (s, C Bzm), 133.2 (s, C Bzm), 128.4 (q, JC—F=270.4 Hz, CF3) 122.0 (s, CH Bzm), 121.8 (s, CH Bzm), 121.7 (s, CH Bzm), 121.4 (s, CH Bzm), 119.0 (q, JC—F=30.7 Hz, CCF3) 118.5 (s, CH Ph), 110.14 (s, CH Bzm), 110.08 (s, CH Bzm), 109.30 (s, CH Bzm), 109.28 (s, CH Bzm), 107.0 (s, CH Ph), 103.1 (q, JC—F=3.8 Hz, CH Ph), 32.8 (s, CH3), 32.7 (s, CH3). 19F NMR (282 MHz, C6D6, 293K): δ −57.1 (CF3).
  • According to an aspect of the present disclosure, a method of making an osmium(II) complex having Formula I
  • L1-Os-L2, wherein L1 and L2 are independently a biscarbene tridentate ligand, wherein L1 and L2 can be same or different is disclosed. The method comprises: (a) reacting a precursor of ligand L1 with an osmium precursor to form an intermediate product, wherein the osmium precursor having the formula OsHx(PR3)y, wherein x is an integer from 2 to 6 and y is an integer from 2 to 5, and R is selected from the group consisting of aryl, alkyl and cycloalkyl; and (b) reacting a precursor of ligand L2 with said intermediate product.
  • In one embodiment of the method, L1 and L2 are monoanionic ligands. In some embodiments, L1 and L2 are independently selected from ligands having Formula II:
  • Figure US20170250354A1-20170831-C00009
  • wherein Y1, Y2 and Y3 comprise C or N; wherein R3 and R4 may represent mono-, or di-substitutions, or no substitution; wherein R5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R1, R2, R3, R4 and R5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents of R1, R2, R3, R4 and R5 are optionally joined to form a ring; and wherein the dash lines show the connection points to osmium.
  • In one embodiment of the method, Y1, Y2 and Y3 comprise C. In one embodiment, Y1 and Y3 comprise C, and Y2 is N. In one embodiment, Y1 and Y3 are N, and Y2 comprise C. In one embodiment, R1 and R2 are independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and partially or fully deuterated variants thereof. In one embodiment, R1 and R2 are independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.
  • In one embodiment of the method, the osmium precursor having the formula OsH6(PR3)2. In another embodiment, R in the osmium precursor having the formula OsHx(PR3)y is selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, and 2-methylphenyl. In other embodiment, R is 1-methylethyl.
  • In another embodiment, the ligands having Formula II are selected from the group consisting of:
  • Figure US20170250354A1-20170831-C00010
    Figure US20170250354A1-20170831-C00011
    Figure US20170250354A1-20170831-C00012
    Figure US20170250354A1-20170831-C00013
    Figure US20170250354A1-20170831-C00014
    Figure US20170250354A1-20170831-C00015
    Figure US20170250354A1-20170831-C00016
    Figure US20170250354A1-20170831-C00017
    Figure US20170250354A1-20170831-C00018
    Figure US20170250354A1-20170831-C00019
    Figure US20170250354A1-20170831-C00020
    Figure US20170250354A1-20170831-C00021
    Figure US20170250354A1-20170831-C00022
    Figure US20170250354A1-20170831-C00023
    Figure US20170250354A1-20170831-C00024
    Figure US20170250354A1-20170831-C00025
  • According to an embodiment, a compound having a structure according to Formula I, L1-Os-L2 is provided, wherein L1 and L2 are different; wherein L1 and L2 are independently selected from ligands having Formula II,
  • Figure US20170250354A1-20170831-C00026
  • In Formula II, Y1, Y2 and Y3 comprise C or N; wherein R3 and R4 may represent mono-, or di-substitutions, or no substitution; wherein R5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R1 and R2 are independently selected from the group consisting of alkyl and cycloalkyl; wherein R3, R4 and R5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof; wherein any two adjacent substituents of R1, R2, R3, R4 and R5 are optionally joined to condense into a fused ring; and wherein the dash lines show the connection points to osmium.
  • In an embodiment of the compound, Y1, Y2 and Y3 comprise C. In one embodiment of the compound, Y1 and Y3 comprise C, and Y2 is N. In some embodiments, Y1 and Y3 are N, and Y2 comprise C. In one embodiment, R1 and R2 are independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and partially or fully deuterated variants thereof. In one embodiment, R1 and R2 are independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.
  • In some embodiments of the compound, L1 and L2 are independently selected from ligands having Formula III:
  • Figure US20170250354A1-20170831-C00027
  • wherein X1, X2, X3, X4, X5, X6, X7 and X8 comprise C or N. In one embodiment, X1, X2, X3, X4, X5, X6, X7 and X8 comprise C.
  • In some embodiments, the ligands having Formula II are selected from the group consisting of: L101 to L159 defined herein.
  • In some embodiments, the compound having a structure according to Formula I, L1-Os-L2 is selected from the group consisting of Compounds 1 to 1159 defined in Table 1 below:
  • TABLE 1
    Compound Number L1 L2
    1. L101 L102
    2. L101 L103
    3. L101 L104
    4. L101 L105
    5. L101 L106
    6. L101 L107
    7. L101 L108
    8. L101 L109
    9. L101 L110
    10. L101 L111
    11. L101 L112
    12. L101 L113
    13. L101 L114
    14. L101 L115
    15. L101 L116
    16. L101 L117
    17. L101 L118
    18. L101 L119
    19. L101 L120
    20. L101 L121
    21. L101 L122
    22. L101 L123
    23. L101 L124
    24. L101 L125
    25. L101 L126
    26. L101 L127
    27. L101 L128
    28. L101 L129
    29. L101 L130
    30. L101 L131
    31. L101 L132
    32. L101 L133
    33. L101 L134
    34. L101 L135
    35. L101 L136
    36. L101 L137
    37. L101 L138
    38. L101 L139
    39. L101 L140
    40. L101 L141
    41. L101 L142
    42. L101 L143
    43. L101 L144
    44. L101 L145
    45. L101 L146
    46. L101 L147
    47. L101 L148
    48. L101 L149
    49. L101 L150
    50. L101 L151
    51. L101 L152
    52. L101 L153
    53. L101 L154
    54. L101 L155
    55. L101 L156
    56. L101 L157
    57. L101 L158
    58. L101 L159
    59. L102 L103
    60. L102 L104
    61. L102 L105
    62. L102 L106
    63. L102 L107
    64. L102 L108
    65. L102 L109
    66. L102 L110
    67. L102 L111
    68. L102 L112
    69. L102 L113
    70. L102 L114
    71. L102 L115
    72. L102 L116
    73. L102 L117
    74. L102 L118
    75. L102 L119
    76. L102 L120
    77. L102 L121
    78. L102 L122
    79. L102 L123
    80. L102 L124
    81. L102 L125
    82. L102 L126
    83. L102 L127
    84. L102 L128
    85. L102 L129
    86. L102 L130
    87. L102 L131
    88. L102 L132
    89. L102 L133
    90. L102 L134
    91. L102 L135
    92. L102 L136
    93. L102 L137
    94. L102 L138
    95. L102 L139
    96. L102 L140
    97. L102 L141
    98. L102 L142
    99. L102 L143
    100. L102 L144
    101. L102 L145
    102. L102 L146
    103. L102 L147
    104. L102 L148
    105. L102 L149
    106. L102 L150
    107. L102 L151
    108. L102 L152
    109. L102 L153
    110. L102 L154
    111. L102 L155
    112. L102 L156
    113. L102 L157
    114. L102 L158
    115. L102 L159
    116. L103 L104
    117. L103 L105
    118. L103 L106
    119. L103 L107
    120. L103 L108
    121. L103 L109
    122. L103 L110
    123. L103 L111
    124. L103 L112
    125. L103 L113
    126. L103 L114
    127. L103 L115
    128. L103 L116
    129. L103 L117
    130. L103 L118
    131. L103 L119
    132. L103 L120
    133. L103 L121
    134. L103 L122
    135. L103 L123
    136. L103 L124
    137. L103 L125
    138. L103 L126
    139. L103 L127
    140. L103 L128
    141. L103 L129
    142. L103 L130
    143. L103 L131
    144. L103 L132
    145. L103 L133
    146. L103 L134
    147. L103 L135
    148. L103 L136
    149. L103 L137
    150. L103 L138
    151. L103 L139
    152. L103 L140
    153. L103 L141
    154. L103 L142
    155. L103 L143
    156. L103 L144
    157. L103 L145
    158. L103 L146
    159. L103 L147
    160. L103 L148
    161. L103 L149
    162. L103 L150
    163. L103 L151
    164. L103 L152
    165. L103 L153
    166. L103 L154
    167. L103 L155
    168. L103 L156
    169. L103 L157
    170. L103 L158
    171. L103 L159
    172. L104 L105
    173. L104 L106
    174. L104 L107
    175. L104 L108
    176. L104 L109
    177. L104 L110
    178. L104 L111
    179. L104 L112
    180. L104 L113
    181. L104 L114
    182. L104 L115
    183. L104 L116
    184. L104 L117
    185. L104 L118
    186. L104 L119
    187. L104 L120
    188. L104 L121
    189. L104 L122
    190. L104 L123
    191. L104 L124
    192. L104 L125
    193. L104 L126
    194. L104 L127
    195. L104 L128
    196. L104 L129
    197. L104 L130
    198. L104 L131
    199. L104 L132
    200. L104 L133
    201. L104 L134
    202. L104 L135
    203. L104 L136
    204. L104 L137
    205. L104 L138
    206. L104 L139
    207. L104 L140
    208. L104 L141
    209. L104 L142
    210. L104 L143
    211. L104 L144
    212. L104 L145
    213. L104 L146
    214. L104 L147
    215. L104 L148
    216. L104 L149
    217. L104 L150
    218. L104 L151
    219. L104 L152
    220. L104 L153
    221. L104 L154
    222. L104 L155
    223. L104 L156
    224. L104 L157
    225. L104 L158
    226. L104 L159
    227. L105 L106
    228. L105 L107
    229. L105 L108
    230. L105 L109
    231. L105 L110
    232. L105 L111
    233. L105 L112
    234. L105 L113
    235. L105 L114
    236. L105 L115
    237. L105 L116
    238. L105 L117
    239. L105 L118
    240. L105 L119
    241. L105 L120
    242. L105 L121
    243. L105 L122
    244. L105 L123
    245. L105 L124
    246. L105 L125
    247. L105 L126
    248. L105 L127
    249. L105 L128
    250. L105 L129
    251. L105 L130
    252. L105 L131
    253. L105 L132
    254. L105 L133
    255. L105 L134
    256. L105 L135
    257. L105 L136
    258. L105 L137
    259. L105 L138
    260. L105 L139
    261. L105 L140
    262. L105 L141
    263. L105 L142
    264. L105 L143
    265. L105 L144
    266. L105 L145
    267. L105 L146
    268. L105 L147
    269. L105 L148
    270. L105 L149
    271. L105 L150
    272. L105 L151
    273. L105 L152
    274. L105 L153
    275. L105 L154
    276. L105 L155
    277. L105 L156
    278. L105 L157
    279. L105 L158
    280. L105 L159
    281. L106 L107
    282. L106 L108
    283. L106 L109
    284. L106 L110
    285. L106 L111
    286. L106 L112
    287. L106 L113
    288. L106 L114
    289. L106 L115
    290. L106 L116
    291. L106 L117
    292. L106 L118
    293. L106 L119
    294. L106 L120
    295. L106 L121
    296. L106 L122
    297. L106 L123
    298. L106 L124
    299. L106 L125
    300. L106 L126
    301. L106 L127
    302. L106 L128
    303. L106 L129
    304. L106 L130
    305. L106 L131
    306. L106 L132
    307. L106 L133
    308. L106 L134
    309. L106 L135
    310. L106 L136
    311. L106 L137
    312. L106 L138
    313. L106 L139
    314. L106 L140
    315. L106 L141
    316. L106 L142
    317. L106 L143
    318. L106 L144
    319. L106 L145
    320. L106 L146
    321. L106 L147
    322. L106 L148
    323. L106 L149
    324. L106 L150
    325. L106 L151
    326. L106 L152
    327. L106 L153
    328. L106 L154
    329. L106 L155
    330. L106 L156
    331. L106 L157
    332. L106 L158
    333. L106 L159
    334. L107 L108
    335. L107 L109
    336. L107 L110
    337. L107 L111
    338. L107 L112
    339. L107 L113
    340. L107 L114
    341. L107 L115
    342. L107 L116
    343. L107 L117
    344. L107 L118
    345. L107 L119
    346. L107 L120
    347. L107 L121
    348. L107 L122
    349. L107 L123
    350. L107 L124
    351. L107 L125
    352. L107 L126
    353. L107 L127
    354. L107 L128
    355. L107 L129
    356. L107 L130
    357. L107 L131
    358. L107 L132
    359. L107 L133
    360. L107 L134
    361. L107 L135
    362. L107 L136
    363. L107 L137
    364. L107 L138
    365. L107 L139
    366. L107 L140
    367. L107 L141
    368. L107 L142
    369. L107 L143
    370. L107 L144
    371. L107 L145
    372. L107 L146
    373. L107 L147
    374. L107 L148
    375. L107 L149
    376. L107 L150
    377. L107 L151
    378. L107 L152
    379. L107 L153
    380. L107 L154
    381. L107 L155
    382. L107 L156
    383. L107 L157
    384. L107 L158
    385. L107 L159
    386. L108 L109
    387. L108 L110
    388. L108 L111
    389. L108 L112
    390. L108 L113
    391. L108 L114
    392. L108 L115
    393. L108 L116
    394. L108 L117
    395. L108 L118
    396. L108 L119
    397. L108 L120
    398. L108 L121
    399. L108 L122
    400. L108 L123
    401. L108 L124
    402. L108 L125
    403. L108 L126
    404. L108 L127
    405. L108 L128
    406. L108 L129
    407. L108 L130
    408. L108 L131
    409. L108 L132
    410. L108 L133
    411. L108 L134
    412. L108 L135
    413. L108 L136
    414. L108 L137
    415. L108 L138
    416. L108 L139
    417. L108 L140
    418. L108 L141
    419. L108 L142
    420. L108 L143
    421. L108 L144
    422. L108 L145
    423. L108 L146
    424. L108 L147
    425. L108 L148
    426. L108 L149
    427. L108 L150
    428. L108 L151
    429. L108 L152
    430. L108 L153
    431. L108 L154
    432. L108 L155
    433. L108 L156
    434. L108 L157
    435. L108 L158
    436. L108 L159
    437. L109 L110
    438. L109 L111
    439. L109 L112
    440. L109 L113
    441. L109 L114
    442. L109 L115
    443. L109 L116
    444. L109 L117
    445. L109 L118
    446. L109 L119
    447. L109 L120
    448. L109 L121
    449. L109 L122
    450. L109 L123
    451. L109 L124
    452. L109 L125
    453. L109 L126
    454. L109 L127
    455. L109 L128
    456. L109 L129
    457. L109 L130
    458. L109 L131
    459. L109 L132
    460. L109 L133
    461. L109 L134
    462. L109 L135
    463. L109 L136
    464. L109 L137
    465. L109 L138
    466. L109 L139
    467. L109 L140
    468. L109 L141
    469. L109 L142
    470. L109 L143
    471. L109 L144
    472. L109 L145
    473. L109 L146
    474. L109 L147
    475. L109 L148
    476. L109 L149
    477. L109 L150
    478. L109 L151
    479. L109 L152
    480. L109 L153
    481. L109 L154
    482. L109 L155
    483. L109 L156
    484. L109 L157
    485. L109 L158
    486. L109 L159
    487. L110 L111
    488. L110 L112
    489. L110 L113
    490. L110 L114
    491. L110 L115
    492. L110 L116
    493. L110 L117
    494. L110 L118
    495. L110 L119
    496. L110 L120
    497. L110 L121
    498. L110 L122
    499. L110 L123
    500. L110 L124
    501. L110 L125
    502. L110 L126
    503. L110 L127
    504. L110 L128
    505. L110 L129
    506. L110 L130
    507. L110 L131
    508. L110 L132
    509. L110 L133
    510. L110 L134
    511. L110 L135
    512. L110 L136
    513. L110 L137
    514. L110 L138
    515. L110 L139
    516. L110 L140
    517. L110 L141
    518. L110 L142
    519. L110 L143
    520. L110 L144
    521. L110 L145
    522. L110 L146
    523. L110 L147
    524. L110 L148
    525. L110 L149
    526. L110 L150
    527. L110 L151
    528. L110 L152
    529. L110 L153
    530. L110 L154
    531. L110 L155
    532. L110 L156
    533. L110 L157
    534. L110 L158
    535. L110 L159
    536. L111 L112
    537. L111 L113
    538. L111 L114
    539. L111 L115
    540. L111 L116
    541. L111 L117
    542. L111 L118
    543. L111 L119
    544. L111 L120
    545. L111 L121
    546. L111 L122
    547. L111 L123
    548. L111 L124
    549. L111 L125
    550. L111 L126
    551. L111 L127
    552. L111 L128
    553. L111 L129
    554. L111 L130
    555. L111 L131
    556. L111 L132
    557. L111 L133
    558. L111 L134
    559. L111 L135
    560. L111 L136
    561. L111 L137
    562. L111 L138
    563. L111 L139
    564. L111 L140
    565. L111 L141
    566. L111 L142
    567. L111 L143
    568. L111 L144
    569. L111 L145
    570. L111 L146
    571. L111 L147
    572. L111 L148
    573. L111 L149
    574. L111 L150
    575. L111 L151
    576. L111 L152
    577. L111 L153
    578. L111 L154
    579. L111 L155
    580. L111 L156
    581. L111 L157
    582. L111 L158
    583. L111 L159
    584. L112 L113
    585. L112 L114
    586. L112 L115
    587. L112 L116
    588. L112 L117
    589. L112 L118
    590. L112 L119
    591. L112 L120
    592. L112 L121
    593. L112 L122
    594. L112 L123
    595. L112 L124
    596. L112 L125
    597. L112 L126
    598. L112 L127
    599. L112 L128
    600. L112 L129
    601. L112 L130
    602. L112 L131
    603. L112 L132
    604. L112 L133
    605. L112 L134
    606. L112 L135
    607. L112 L136
    608. L112 L137
    609. L112 L138
    610. L112 L139
    611. L112 L140
    612. L112 L141
    613. L112 L142
    614. L112 L143
    615. L112 L144
    616. L112 L145
    617. L112 L146
    618. L112 L147
    619. L112 L148
    620. L112 L149
    621. L112 L150
    622. L112 L151
    623. L112 L152
    624. L112 L153
    625. L112 L154
    626. L112 L155
    627. L112 L156
    628. L112 L157
    629. L112 L158
    630. L112 L159
    631. L113 L114
    632. L113 L115
    633. L113 L116
    634. L113 L117
    635. L113 L118
    636. L113 L119
    637. L113 L120
    638. L113 L121
    639. L113 L122
    640. L113 L123
    641. L113 L124
    642. L113 L125
    643. L113 L126
    644. L113 L127
    645. L113 L128
    646. L113 L129
    647. L113 L130
    648. L113 L131
    649. L113 L132
    650. L113 L133
    651. L113 L134
    652. L113 L135
    653. L113 L136
    654. L113 L137
    655. L113 L138
    656. L113 L139
    657. L113 L140
    658. L113 L141
    659. L113 L142
    660. L113 L143
    661. L113 L144
    662. L113 L145
    663. L113 L146
    664. L113 L147
    665. L113 L148
    666. L113 L149
    667. L113 L150
    668. L113 L151
    669. L113 L152
    670. L113 L153
    671. L113 L154
    672. L113 L155
    673. L113 L156
    674. L113 L157
    675. L113 L158
    676. L113 L159
    677. L114 L115
    678. L114 L116
    679. L114 L117
    680. L114 L118
    681. L114 L119
    682. L114 L120
    683. L114 L121
    684. L114 L122
    685. L114 L123
    686. L114 L124
    687. L114 L125
    688. L114 L126
    689. L114 L127
    690. L114 L128
    691. L114 L129
    692. L114 L130
    693. L114 L131
    694. L114 L132
    695. L114 L133
    696. L114 L134
    697. L114 L135
    698. L114 L136
    699. L114 L137
    700. L114 L138
    701. L114 L139
    702. L114 L140
    703. L114 L141
    704. L114 L142
    705. L114 L143
    706. L114 L144
    707. L114 L145
    708. L114 L146
    709. L114 L147
    710. L114 L148
    711. L114 L149
    712. L114 L150
    713. L114 L151
    714. L114 L152
    715. L114 L153
    716. L114 L154
    717. L114 L155
    718. L114 L156
    719. L114 L157
    720. L114 L158
    721. L114 L159
    722. L115 L116
    723. L115 L117
    724. L115 L118
    725. L115 L119
    726. L115 L120
    727. L115 L121
    728. L115 L122
    729. L115 L123
    730. L115 L124
    731. L115 L125
    732. L115 L126
    733. L115 L127
    734. L115 L128
    735. L115 L129
    736. L115 L130
    737. L115 L131
    738. L115 L132
    739. L115 L133
    740. L115 L134
    741. L115 L135
    742. L115 L136
    743. L115 L137
    744. L115 L138
    745. L115 L139
    746. L115 L140
    747. L115 L141
    748. L115 L142
    749. L115 L143
    750. L115 L144
    751. L115 L145
    752. L115 L146
    753. L115 L147
    754. L115 L148
    755. L115 L149
    756. L115 L150
    757. L115 L151
    758. L115 L152
    759. L115 L153
    760. L115 L154
    761. L115 L155
    762. L115 L156
    763. L115 L157
    764. L115 L158
    765. L115 L159
    766. L116 L117
    767. L116 L118
    768. L116 L119
    769. L116 L120
    770. L116 L121
    771. L116 L122
    772. L116 L123
    773. L116 L124
    774. L116 L125
    775. L116 L126
    776. L116 L127
    777. L116 L128
    778. L116 L129
    779. L116 L130
    780. L116 L131
    781. L116 L132
    782. L116 L133
    783. L116 L134
    784. L116 L135
    785. L116 L136
    786. L116 L137
    787. L116 L138
    788. L116 L139
    789. L116 L140
    790. L116 L141
    791. L116 L142
    792. L116 L143
    793. L116 L144
    794. L116 L145
    795. L116 L146
    796. L116 L147
    797. L116 L148
    798. L116 L149
    799. L116 L150
    800. L116 L151
    801. L116 L152
    802. L116 L153
    803. L116 L154
    804. L116 L155
    805. L116 L156
    806. L116 L157
    807. L116 L158
    808. L116 L159
    809. L117 L118
    810. L117 L119
    811. L117 L120
    812. L117 L121
    813. L117 L122
    814. L117 L123
    815. L117 L124
    816. L117 L125
    817. L117 L126
    818. L117 L127
    819. L117 L128
    820. L117 L129
    821. L117 L130
    822. L117 L131
    823. L117 L132
    824. L117 L133
    825. L117 L134
    826. L117 L135
    827. L117 L136
    828. L117 L137
    829. L117 L138
    830. L117 L139
    831. L117 L140
    832. L117 L141
    833. L117 L142
    834. L117 L143
    835. L117 L144
    836. L117 L145
    837. L117 L146
    838. L117 L147
    839. L117 L148
    840. L117 L149
    841. L117 L150
    842. L117 L151
    843. L117 L152
    844. L117 L153
    845. L117 L154
    846. L117 L155
    847. L117 L156
    848. L117 L157
    849. L117 L158
    850. L117 L159
    851. L118 L119
    852. L118 L120
    853. L118 L121
    854. L118 L122
    855. L118 L123
    856. L118 L124
    857. L118 L125
    858. L118 L126
    859. L118 L127
    860. L118 L128
    861. L118 L129
    862. L118 L130
    863. L118 L131
    864. L118 L132
    865. L118 L133
    866. L118 L134
    867. L118 L135
    868. L118 L136
    869. L118 L137
    870. L118 L138
    871. L118 L139
    872. L118 L140
    873. L118 L141
    874. L118 L142
    875. L118 L143
    876. L118 L144
    877. L118 L145
    878. L118 L146
    879. L118 L147
    880. L118 L148
    881. L118 L149
    882. L118 L150
    883. L118 L151
    884. L118 L152
    885. L118 L153
    886. L118 L154
    887. L118 L155
    888. L118 L156
    889. L118 L157
    890. L118 L158
    891. L118 L159
    892. L119 L120
    893. L119 L121
    894. L119 L122
    895. L119 L123
    896. L119 L124
    897. L119 L125
    898. L119 L126
    899. L119 L127
    900. L119 L128
    901. L119 L129
    902. L119 L130
    903. L119 L131
    904. L119 L132
    905. L119 L133
    906. L119 L134
    907. L119 L135
    908. L119 L136
    909. L119 L137
    910. L119 L138
    911. L119 L139
    912. L119 L140
    913. L119 L141
    914. L119 L142
    915. L119 L143
    916. L119 L144
    917. L119 L145
    918. L119 L146
    919. L119 L147
    920. L119 L148
    921. L119 L149
    922. L119 L150
    923. L119 L151
    924. L119 L152
    925. L119 L153
    926. L119 L154
    927. L119 L155
    928. L119 L156
    929. L119 L157
    930. L119 L158
    931. L119 L159
    932. L120 L121
    933. L120 L122
    934. L120 L123
    935. L120 L124
    936. L120 L125
    937. L120 L126
    938. L120 L127
    939. L120 L128
    940. L120 L129
    941. L120 L130
    942. L120 L131
    943. L120 L132
    944. L120 L133
    945. L120 L134
    946. L120 L135
    947. L120 L136
    948. L120 L137
    949. L120 L138
    950. L120 L139
    951. L120 L140
    952. L120 L141
    953. L120 L142
    954. L120 L143
    955. L120 L144
    956. L120 L145
    957. L120 L146
    958. L120 L147
    959. L120 L148
    960. L120 L149
    961. L120 L150
    962. L120 L151
    963. L120 L152
    964. L120 L153
    965. L120 L154
    966. L120 L155
    967. L120 L156
    968. L120 L157
    969. L120 L158
    970. L120 L159
    971. L121 L122
    972. L121 L123
    973. L121 L124
    974. L121 L125
    975. L121 L126
    976. L121 L127
    977. L121 L128
    978. L121 L129
    979. L121 L130
    980. L121 L131
    981. L121 L132
    982. L121 L133
    983. L121 L134
    984. L121 L135
    985. L121 L136
    986. L121 L137
    987. L121 L138
    988. L121 L139
    989. L121 L140
    990. L121 L141
    991. L121 L142
    992. L121 L143
    993. L121 L144
    994. L121 L145
    995. L121 L146
    996. L121 L147
    997. L121 L148
    998. L121 L149
    999. L121 L150
    1000. L121 L151
    1001. L121 L152
    1002. L121 L153
    1003. L121 L154
    1004. L121 L155
    1005. L121 L156
    1006. L121 L157
    1007. L121 L158
    1008. L121 L159
    1009. L122 L123
    1010. L122 L124
    1011. L122 L125
    1012. L122 L126
    1013. L122 L127
    1014. L122 L128
    1015. L122 L129
    1016. L122 L130
    1017. L122 L131
    1018. L122 L132
    1019. L122 L133
    1020. L122 L134
    1021. L122 L135
    1022. L122 L136
    1023. L122 L137
    1024. L122 L138
    1025. L122 L139
    1026. L122 L140
    1027. L122 L141
    1028. L122 L142
    1029. L122 L143
    1030. L122 L144
    1031. L122 L145
    1032. L122 L146
    1033. L122 L147
    1034. L122 L148
    1035. L122 L149
    1036. L122 L150
    1037. L122 L151
    1038. L122 L152
    1039. L122 L153
    1040. L122 L154
    1041. L122 L155
    1042. L122 L156
    1043. L122 L157
    1044. L122 L158
    1045. L122 L159
    1046. L123 L124
    1047. L123 L125
    1048. L123 L126
    1049. L123 L127
    1050. L123 L128
    1051. L123 L129
    1052. L123 L130
    1053. L123 L131
    1054. L123 L132
    1055. L123 L133
    1056. L123 L134
    1057. L123 L135
    1058. L123 L136
    1059. L123 L137
    1060. L123 L138
    1061. L123 L139
    1062. L123 L140
    1063. L123 L141
    1064. L123 L142
    1065. L123 L143
    1066. L123 L144
    1067. L123 L145
    1068. L123 L146
    1069. L123 L147
    1070. L123 L148
    1071. L123 L149
    1072. L123 L150
    1073. L123 L151
    1074. L123 L152
    1075. L123 L153
    1076. L123 L154
    1077. L123 L155
    1078. L123 L156
    1079. L123 L157
    1080. L123 L158
    1081. L123 L159
    1082. L124 L125
    1083. L124 L126
    1084. L124 L127
    1085. L124 L128
    1086. L124 L129
    1087. L124 L130
    1088. L124 L131
    1089. L124 L132
    1090. L124 L133
    1091. L124 L134
    1092. L124 L135
    1093. L124 L136
    1094. L124 L137
    1095. L124 L138
    1096. L124 L139
    1097. L124 L140
    1098. L124 L141
    1099. L124 L142
    1100. L124 L143
    1101. L124 L144
    1102. L124 L145
    1103. L124 L146
    1104. L124 L147
    1105. L124 L148
    1106. L124 L149
    1107. L124 L150
    1108. L124 L151
    1109. L124 L152
    1110. L124 L153
    1111. L124 L154
    1112. L124 L155
    1113. L124 L156
    1114. L124 L157
    1115. L124 L158
    1116. L124 L159
    1117. L125 L126
    1118. L125 L127
    1119. L125 L128
    1120. L125 L129
    1121. L125 L130
    1122. L125 L131
    1123. L125 L132
    1124. L125 L133
    1125. L125 L134
    1126. L125 L135
    1127. L125 L136
    1128. L125 L137
    1129. L125 L138
    1130. L125 L139
    1131. L125 L140
    1132. L125 L141
    1133. L125 L142
    1134. L125 L143
    1135. L125 L144
    1136. L125 L145
    1137. L125 L146
    1138. L125 L147
    1139. L125 L148
    1140. L125 L149
    1141. L125 L150
    1142. L125 L151
    1143. L125 L152
    1144. L125 L153
    1145. L125 L154
    1146. L125 L155
    1147. L125 L156
    1148. L125 L157
    1149. L125 L158
    1150. L125 L159
  • In one embodiment, a first device comprising a first organic light emitting device is disclosed. The first organic light emitting device comprises an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound having the structure according Formula I, L1-Os-L2; wherein L1 and L2 are different; wherein L1 and L2 are independently selected from ligands having Formula II:
  • Figure US20170250354A1-20170831-C00028
  • wherein Y1, Y2 and Y3 comprise C or N; wherein R3 and R4 may represent mono-, or di-substitutions, or no substitution; wherein R5 may represent mono-, di-, or tri-substitutions, or no substitution; wherein R1 and R2 are independently selected from the group consisting of alkyl and cycloalkyl; wherein R3, R4 and R5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof; wherein any two adjacent substituents of R1, R2, R3, R4 and R5 are optionally joined to condense into a fused ring; and wherein the dash lines show the connection points to osmium.
  • In one embodiment of the first device, Y1, Y2 and Y3 comprise C. In one embodiment, Y1, Y2 and Y3 are N. In one embodiment, R1 and R2 are independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.
  • In some embodiments of the first device, L1 and L2 are independently selected from ligands having Formula III:
  • Figure US20170250354A1-20170831-C00029
  • wherein X1, X2, X3, X4, X5, X6, X7 and X8 comprise C or N. In some embodiments, X1, X2, X3, X4, X5, X6, X7 and X8 comprise C.
  • In some embodiments of the first device, the ligands having Formula II are selected from the group consisting of L101 to L159 defined herein.
  • In some embodiments of the first device, the first emitting compound is selected from the group consisting of Compounds 1 to 1159 defined in Table 1.
  • The first device can be one or more of a consumer product, an organic light-emitting device, and/or a lighting panel.
  • The organic layer in the organic light emitting device can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
  • The organic layer can also include a host. In some embodiments, the host can include a metal complex. In one embodiment, the host can be a metal 8-hydroxyquinolate. The host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the host can be an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡C—CnH2n+1, Ar1, Ar1—Ar2, CnH2n—Ar1, or no substitution. In the preceding substituents n can range from 1 to 10; and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
  • The host can be a compound selected from the group consisting of carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. The “aza” designation in the fragments described above, i.e., aza-dibenzofuran, aza-dibenzonethiophene, etc., means that one or more of the C—H groups in the respective fragment can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein. The host can include a metal complex. The host can be a specific compound selected from the group consisting of:
  • Figure US20170250354A1-20170831-C00030
    Figure US20170250354A1-20170831-C00031
  • and combinations thereof.
  • In yet another aspect of the present disclosure, a formulation comprising the compound having a structure according to Formula I, L1-Os-L2, as defined herein, is disclosed. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, and an electron transport layer material, disclosed herein.
  • Combination with Other Materials
  • The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
    • HIL/HTL:
  • A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but not limit to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
  • Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
  • Figure US20170250354A1-20170831-C00032
  • Each of Ar1 to Ar9 is selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
  • In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:
  • Figure US20170250354A1-20170831-C00033
  • wherein k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.
  • Examples of metal complexes used in HIL or HTL include, but not limit to the following general formula:
  • Figure US20170250354A1-20170831-C00034
  • wherein Met is a metal, which can have an atomic weight greater than 40; (Y101-Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
  • In one aspect, (Y101-Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101-Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.
    • Host:
  • The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.
  • Examples of metal complexes used as host are preferred to have the following general formula:
  • Figure US20170250354A1-20170831-C00035
  • wherein Met is a metal; (Y103-Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L11 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
  • In one aspect, the metal complexes are:
  • Figure US20170250354A1-20170831-C00036
  • wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
  • In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103-Y104) is a carbene ligand.
  • Examples of organic compounds used as host are selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
  • In one aspect, host compound contains at least one of the following groups in the molecule:
  • Figure US20170250354A1-20170831-C00037
    Figure US20170250354A1-20170831-C00038
  • wherein R101 to R107 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above k is an integer from 0 to 20 or 1 to 20; k′″ is an integer from 0 to 20. X101 to X108 is selected from C (including CH) or N. Z101 and Z102 is selected from NR101, O, or S.
    • HBL:
  • A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. 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.
  • In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
  • In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
  • Figure US20170250354A1-20170831-C00039
  • wherein k is an integer from 1 to 20; L101 is an another ligand, k′ is an integer from 1 to 3.
    • ETL:
  • Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
  • In one aspect, compound used in ETL contains at least one of the following groups in the molecule:
  • Figure US20170250354A1-20170831-C00040
  • wherein R101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar1 to Ar3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X101 to X108 is selected from C (including CH) or N.
  • In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:
  • Figure US20170250354A1-20170831-C00041
  • wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
  • In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.
  • In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exciton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table 2 below. Table 2 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.
  • TABLE 2
    MATERIAL EXAMPLES OF MATERIAL PUBLICATIONS
    Hole injection materials
    Phthalocyanine and porphryin compounds
    Figure US20170250354A1-20170831-C00042
         		Appl. Phys. Lett. 69, 2160 (1996)
    Starburst triarylamines
    Figure US20170250354A1-20170831-C00043
         		J. Lumin. 72-74, 985 (1997)
    CFx Fluorohydrocarbon polymer
    Figure US20170250354A1-20170831-C00044
         		Appl. Phys. Lett. 78, 673 (2001)
    Conducting polymers (e.g., PEDOT:PSS, polyaniline, polypthiophene)
    Figure US20170250354A1-20170831-C00045
         		Synth. Met. 87, 171 (1997) WO2007002683
    Phosphonic acid and sliane SAMs
    Figure US20170250354A1-20170831-C00046
         		US20030162053
    Triarylamine or polythiophene polymers with conductivity dopants
    Figure US20170250354A1-20170831-C00047
         		EP1725079A1
    Figure US20170250354A1-20170831-C00048
    Figure US20170250354A1-20170831-C00049
    Organic compounds with conductive inorganic compounds, such as molybdenum and tungsten oxides
    Figure US20170250354A1-20170831-C00050
         		US20050123751 SID Symposium Digest, 37, 923 (2006) WO2009018009
    n-type semiconducting organic complexes
    Figure US20170250354A1-20170831-C00051
         		US20020158242
    Metal organometallic complexes
    Figure US20170250354A1-20170831-C00052
         		US20060240279
    Cross-linkable compounds
    Figure US20170250354A1-20170831-C00053
         		US20080220265
    Polythiophene based polymers and copolymers
    Figure US20170250354A1-20170831-C00054
         		WO 2011075644 EP2350216
    Hole transporting materials
    Triarylamines (e.g., TPD, α-NPD)
    Figure US20170250354A1-20170831-C00055
         		Appl. Phys. Lett. 51, 913 (1987)
    Figure US20170250354A1-20170831-C00056
         		U.S. Pat. No. 5,061,569
    Figure US20170250354A1-20170831-C00057
         		EP650955
    Figure US20170250354A1-20170831-C00058
         		J. Mater. Chem. 3, 319 (1993)
    Figure US20170250354A1-20170831-C00059
         		Appl. Phys. Lett. 90, 183503 (2007)
    Figure US20170250354A1-20170831-C00060
         		Appl. Phys. Lett. 90, 183503 (2007)
    Triaylamine on spirofluorene core
    Figure US20170250354A1-20170831-C00061
         		Synth. Met. 91, 209 (1997)
    Arylamine carbazole compounds
    Figure US20170250354A1-20170831-C00062
         		Adv. Mater. 6, 677 (1994), US20080124572
    Triarylamine with (di)benzothiophene/ (di)benzofuran
    Figure US20170250354A1-20170831-C00063
         		US20070278938, US20080106190 US20110163302
    Indolocarbazoles
    Figure US20170250354A1-20170831-C00064
         		Synth. Met. 111, 421 (2000)
    Isoindole compounds
    Figure US20170250354A1-20170831-C00065
         		Chem. Mater. 15, 3148 (2003)
    Metal carbene complexes
    Figure US20170250354A1-20170831-C00066
         		US20080018221
    Phosphorescent OLED host materials
    Red hosts
    Arylcarbazoles
    Figure US20170250354A1-20170831-C00067
         		Appl. Phys. Lett. 78, 1622 (2001)
    Metal 8-hydroxyquinolates (e.g., Alq3, BAlq)
    Figure US20170250354A1-20170831-C00068
         		Nature 395, 151 (1998)
    Figure US20170250354A1-20170831-C00069
         		US20060202194
    Figure US20170250354A1-20170831-C00070
         		WO2005014551
    Figure US20170250354A1-20170831-C00071
         		WO2006072002
    Metal phenoxybenzothiazole compounds
    Figure US20170250354A1-20170831-C00072
         		Appl. Phys. Lett. 90, 123509 (2007)
    Conjugated oligomers and polymers (e.g., polyfluorene)
    Figure US20170250354A1-20170831-C00073
         		Org. Electron. 1, 15 (2000)
    Aromatic fused rings
    Figure US20170250354A1-20170831-C00074
         		WO2009066779, WO2009066778, WO2009063833, US20090045731, US20090045730, WO2009008311, US20090008605, US20090009065
    Zinc complexes
    Figure US20170250354A1-20170831-C00075
         		WO2010056066
    Chrysene based compounds
    Figure US20170250354A1-20170831-C00076
         		WO2011086863
    Green hosts
    Arylcarbazoles
    Figure US20170250354A1-20170831-C00077
         		Appl. Phys. Lett. 78, 1622 (2001)
    Figure US20170250354A1-20170831-C00078
         		US20030175553
    Figure US20170250354A1-20170831-C00079
         		WO2001039234
    Aryltriphenylene compounds
    Figure US20170250354A1-20170831-C00080
         		US20060280965
    Figure US20170250354A1-20170831-C00081
         		US20060280965
    Figure US20170250354A1-20170831-C00082
         		WO2009021126
    Poly-fused heteroaryl compounds
    Figure US20170250354A1-20170831-C00083
         		US20090309488 US20090302743 US20100012931
    Donor acceptor type molecules
    Figure US20170250354A1-20170831-C00084
         		WO2008056746
    Figure US20170250354A1-20170831-C00085
         		WO2010107244
    Aza-carbazole/DBT/DBF
    Figure US20170250354A1-20170831-C00086
         		JP2008074939
    Figure US20170250354A1-20170831-C00087
         		US20100187984
    Polymers (e.g., PVK)
    Figure US20170250354A1-20170831-C00088
         		Appl. Phys. Lett. 77, 2280 (2000)
    Spirofluorene compounds
    Figure US20170250354A1-20170831-C00089
         		WO2004093207
    Metal phenoxybenzooxazole compounds
    Figure US20170250354A1-20170831-C00090
         		WO2005089025
    Figure US20170250354A1-20170831-C00091
         		WO2006132173
    Figure US20170250354A1-20170831-C00092
         		JP200511610
    Spirofluorene-carbazole compounds
    Figure US20170250354A1-20170831-C00093
         		JP2007254297
    Figure US20170250354A1-20170831-C00094
         		JP2007254297
    Indolocabazoles
    Figure US20170250354A1-20170831-C00095
         		WO2007063796
    Figure US20170250354A1-20170831-C00096
         		WO2007063754
    5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole)
    Figure US20170250354A1-20170831-C00097
         		J. Appl. Phys. 90, 5048 (2001)
    Figure US20170250354A1-20170831-C00098
         		WO2004107822
    Tetraphenylene complexes
    Figure US20170250354A1-20170831-C00099
         		US20050112407
    Metal phenoxypyridine compounds
    Figure US20170250354A1-20170831-C00100
         		WO2005030900
    Metal coordination complexes (e.g., Zn, Al with N{circumflex over ( )}N ligands)
    Figure US20170250354A1-20170831-C00101
         		US20040137268, US20040137267
    Blue hosts
    Arylcarbazoles
    Figure US20170250354A1-20170831-C00102
         		Appl. Phys. Lett, 82, 2422 (2003)
    Figure US20170250354A1-20170831-C00103
         		US20070190359
    Dibenzothiophene/Dibenzo- furan-carbazole compounds
    Figure US20170250354A1-20170831-C00104
         		WO2006114966, US20090167162
    Figure US20170250354A1-20170831-C00105
         		US20090167162
    Figure US20170250354A1-20170831-C00106
         		WO2009086028
    Figure US20170250354A1-20170831-C00107
         		US20090030202, US20090017330
    Figure US20170250354A1-20170831-C00108
         		US20100084966
    Silicon aryl compounds
    Figure US20170250354A1-20170831-C00109
         		US20050238919
    Figure US20170250354A1-20170831-C00110
         		WO2009003898
    Silicon/Germanium aryl compounds
    Figure US20170250354A1-20170831-C00111
         		EP2034538A
    Aryl benzoyl ester
    Figure US20170250354A1-20170831-C00112
         		WO2006100298
    Carbazole linked by non- conjugated groups
    Figure US20170250354A1-20170831-C00113
         		US20040115476
    Aza-carbazoles
    Figure US20170250354A1-20170831-C00114
         		US20060121308
    High triplet metal organometallic complex
    Figure US20170250354A1-20170831-C00115
         		U.S. Pat. No. 7,154,114
    Phosphorescent dopants
    Red dopants
    Heavy metal porphyrins (e.g., PtOEP)
    Figure US20170250354A1-20170831-C00116
         		Nature 395, 151 (1998)
    Iridium(III) organometallic complexes
    Figure US20170250354A1-20170831-C00117
         		Appl. Phys. Lett. 78, 1622 (2001)
    Figure US20170250354A1-20170831-C00118
         		US2006835469
    Figure US20170250354A1-20170831-C00119
         		US2006835469
    Figure US20170250354A1-20170831-C00120
         		US20060202194
    Figure US20170250354A1-20170831-C00121
         		US20060202194
    Figure US20170250354A1-20170831-C00122
         		US20070087321
    Figure US20170250354A1-20170831-C00123
         		US20080261076 US20100090591
    Figure US20170250354A1-20170831-C00124
         		US20070087321
    Figure US20170250354A1-20170831-C00125
         		Adv. Mater. 19, 739 (2007)
    Figure US20170250354A1-20170831-C00126
         		WO2009100991
    Figure US20170250354A1-20170831-C00127
         		WO2008101842
    Figure US20170250354A1-20170831-C00128
         		U.S. Pat. No. 7,232,618
    Platinum(II) organometallic complexes
    Figure US20170250354A1-20170831-C00129
         		WO2003040257
    Figure US20170250354A1-20170831-C00130
         		US20070103060
    Osminum(III) complexes
    Figure US20170250354A1-20170831-C00131
         		Chem. Mater. 17, 3532 (2005)
    Ruthenium(II) complexes
    Figure US20170250354A1-20170831-C00132
         		Adv. Mater. 17, 1059 (2005)
    Rhenium (I), (II), and (III) complexes
    Figure US20170250354A1-20170831-C00133
         		US20050244673
    Green dopants
    Iridium(III) organometallic complexes
    Figure US20170250354A1-20170831-C00134
         		Inorg. Chem. 40, 1704 (2001)
    Figure US20170250354A1-20170831-C00135
         		US20020034656
    Figure US20170250354A1-20170831-C00136
         		U.S. Pat. No. 7,332,232
    Figure US20170250354A1-20170831-C00137
         		US20090108737
    Figure US20170250354A1-20170831-C00138
         		WO2010028151
    Figure US20170250354A1-20170831-C00139
         		EP1841834B
    Figure US20170250354A1-20170831-C00140
         		US20060127696
    Figure US20170250354A1-20170831-C00141
         		US20090039776
    Figure US20170250354A1-20170831-C00142
         		U.S. Pat. No. 6,921,915
    Figure US20170250354A1-20170831-C00143
         		US20100244004
    Figure US20170250354A1-20170831-C00144
         		U.S. Pat. No. 6,687,266
    Figure US20170250354A1-20170831-C00145
         		Chem. Mater. 16, 2480 (2004)
    Figure US20170250354A1-20170831-C00146
         		US20070190359
    Figure US20170250354A1-20170831-C00147
         		US20060008670 JP2007123392
    Figure US20170250354A1-20170831-C00148
         		WO2010086089, WO2011044988
    Figure US20170250354A1-20170831-C00149
         		Adv. Mater. 16, 2003 (2004)
    Figure US20170250354A1-20170831-C00150
         		Angew. Chem. Int. Ed. 2006, 45, 7800
    Figure US20170250354A1-20170831-C00151
         		WO2009050290
    Figure US20170250354A1-20170831-C00152
         		US20090165846
    Figure US20170250354A1-20170831-C00153
         		US20080015355
    Figure US20170250354A1-20170831-C00154
         		US20010015432
    Figure US20170250354A1-20170831-C00155
         		US20100295032
    Monomer for polymeric metal organometallic compounds
    Figure US20170250354A1-20170831-C00156
         		U.S. Pat. No. 7,250,226, U.S. Pat. No. 7,396,598
    Pt(II) organometallic complexes, including polydentated ligands
    Figure US20170250354A1-20170831-C00157
         		Appl. Phys. Lett. 86, 153505 (2005)
    Figure US20170250354A1-20170831-C00158
         		Appl. Phys. Lett. 86, 153505 (2005)
    Figure US20170250354A1-20170831-C00159
         		Chem. Lett. 34, 592 (2005)
    Figure US20170250354A1-20170831-C00160
         		WO2002015645
    Figure US20170250354A1-20170831-C00161
         		US20060263635
    Figure US20170250354A1-20170831-C00162
         		US20060182992 US20070103060
    Cu complexes
    Figure US20170250354A1-20170831-C00163
         		WO2009000673
    Figure US20170250354A1-20170831-C00164
         		US20070111026
    Gold complexes
    Figure US20170250354A1-20170831-C00165
         		Chem. Commun. 2906 (2005)
    Rhenium(III) complexes
    Figure US20170250354A1-20170831-C00166
         		Inorg. Chem. 42, 1248 (2003)
    Osmium(II) complexes
    Figure US20170250354A1-20170831-C00167
         		U.S. Pat. No. 7,279,704
    Deuterated organometallic complexes
    Figure US20170250354A1-20170831-C00168
         		US20030138657
    Organometallic complexes with two or more metal centers
    Figure US20170250354A1-20170831-C00169
         		US20030152802
    Figure US20170250354A1-20170831-C00170
         		U.S. Pat. No. 7,090,928
    Blue dopants
    Iridium(III) organometallic complexes
    Figure US20170250354A1-20170831-C00171
         		WO2002002714
    Figure US20170250354A1-20170831-C00172
         		WO2006009024
    Figure US20170250354A1-20170831-C00173
         		US20060251923 US20110057559 US20110204333
    Figure US20170250354A1-20170831-C00174
         		U.S. Pat. No. 7,393,599, WO2006056418, US20050260441, WO2005019373
    Figure US20170250354A1-20170831-C00175
         		U.S. Pat. No. 7,534,505
    Figure US20170250354A1-20170831-C00176
         		WO2011051404
    Figure US20170250354A1-20170831-C00177
         		U.S. Pat. No. 7,445,855
    Figure US20170250354A1-20170831-C00178
         		US20070190359, US20080297033 US20100148663
    Figure US20170250354A1-20170831-C00179
         		U.S. Pat. No. 7,338,722
    Figure US20170250354A1-20170831-C00180
         		US20020134984
    Figure US20170250354A1-20170831-C00181
         		Angew. Chem. Int. Ed. 47, 4542 (2008)
    Figure US20170250354A1-20170831-C00182
         		Chem. Mater. 18, 5119 (2006)
    Figure US20170250354A1-20170831-C00183
         		Inorg. Chem. 46, 4308 (2007)
    Figure US20170250354A1-20170831-C00184
         		WO2005123873
    Figure US20170250354A1-20170831-C00185
         		WO2005123873
    Figure US20170250354A1-20170831-C00186
         		WO2007004380
    Figure US20170250354A1-20170831-C00187
         		WO2006082742
    Osmium(II) complexes
    Figure US20170250354A1-20170831-C00188
         		U.S. Pat. No. 7,279,704
    Figure US20170250354A1-20170831-C00189
         		Organometallics 23, 3745 (2004)
    Gold complexes
    Figure US20170250354A1-20170831-C00190
         		Appl. Phys. Lett. 74, 1361 (1999)
    Platinum(II) complexes
    Figure US20170250354A1-20170831-C00191
         		WO2006098120, WO2006103874
    Pt tetradentate complexes with at least one metal- carbene bond
    Figure US20170250354A1-20170831-C00192
         		U.S. Pat. No. 7,655,323
    Exciton/hole blocking layer materials
    Bathocuprine compounds (e.g., BCP, BPhen)
    Figure US20170250354A1-20170831-C00193
         		Appl. Phys. Lett. 75, 4 (1999)
    Figure US20170250354A1-20170831-C00194
         		Appl. Phys. Lett. 79, 449 (2001)
    Metal 8-hydroxyquinolates (e.g., BAlq)
    Figure US20170250354A1-20170831-C00195
         		Appl. Phys. Lett. 81, 162 (2002)
    5-member ring electron deficient heterocycles such as triazole, oxadiazole, imidazole, benzoimidazole
    Figure US20170250354A1-20170831-C00196
         		Appl. Phys. Lett. 81, 162 (2002)
    Triphenylene compounds
    Figure US20170250354A1-20170831-C00197
         		US20050025993
    Fluorinated aromatic compounds
    Figure US20170250354A1-20170831-C00198
         		Appl. Phys. Lett. 79, 156 (2001)
    Phenothiazine-S-oxide
    Figure US20170250354A1-20170831-C00199
         		WO2008132085
    Silylated five-membered nitrogen, oxygen, sulfur or phosphorus dibenzoheterocycles
    Figure US20170250354A1-20170831-C00200
         		WO2010079051
    Aza-carbazoles
    Figure US20170250354A1-20170831-C00201
         		US20060121308
    Electron transporting materials
    Anthracene- benzoimidazole compounds
    Figure US20170250354A1-20170831-C00202
         		WO2003060956
    Figure US20170250354A1-20170831-C00203
         		US20090179554
    Aza triphenylene derivatives
    Figure US20170250354A1-20170831-C00204
         		US20090115316
    Anthracene-benzothiazole compounds
    Figure US20170250354A1-20170831-C00205
         		Appl. Phys. Lett. 89, 063504 (2006)
    Metal 8-hydroxyquinolates (e.g., Alq3, Zrq4)
    Figure US20170250354A1-20170831-C00206
         		Appl. Phys. Lett. 51, 913 (1987) U.S. Pat. No. 7,230,107
    Metal hydroxybenoquinolates
    Figure US20170250354A1-20170831-C00207
         		Chem. Lett. 5, 905 (1993)
    Bathocuprine compounds such as BCP, BPhen, etc
    Figure US20170250354A1-20170831-C00208
         		Appl. Phys. Lett. 91, 263503 (2007)
    Figure US20170250354A1-20170831-C00209
         		Appl. Phys. Lett. 79, 449 (2001)
    5-member ring electron deficient heterocycles (e.g.,triazole, oxadiazole, imidazole, benzoimidazole)
    Figure US20170250354A1-20170831-C00210
         		Appl. Phys. Lett. 74, 865 (1999)
    Figure US20170250354A1-20170831-C00211
         		Appl. Phys. Lett. 55, 1489 (1989)
    Figure US20170250354A1-20170831-C00212
         		Jpn. J. Apply. Phys. 32, L917 (1993)
    Silole compounds
    Figure US20170250354A1-20170831-C00213
         		Org. Electron. 4, 113 (2003)
    Arylborane compounds
    Figure US20170250354A1-20170831-C00214
         		J. Am. Chem. Soc. 120, 9714 (1998)
    Fluorinated aromatic compounds
    Figure US20170250354A1-20170831-C00215
         		J. Am. Chem. Soc. 122, 1832 (2000)
    Fullerene (e.g., C60)
    Figure US20170250354A1-20170831-C00216
         		US20090101870
    Triazine complexes
    Figure US20170250354A1-20170831-C00217
         		US20040036077
    Zn (N{circumflex over ( )}N) complexes
    Figure US20170250354A1-20170831-C00218
         		U.S. Pat. No. 6,528,187
  • 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. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.

Claims (20)

We claim:
1. A compound having a structure according to Formula I:

L1-Os-L2;
wherein L1 and L2 are different;
wherein L1 and L2 are independently selected from ligands having Formula II:
Figure US20170250354A1-20170831-C00219
wherein:
1) for L1, Y1, Y2 and Y3 comprise C and, for L2, either (i) Y1 and Y3 comprises C and Y2 is N, or (ii) Y1 and Y3 are N, and Y2 comprises C, or
2) for L1, Y1 and Y3 comprises C and Y2 is N, and, for L2, Y1 and Y3 are N, and Y2 comprises C;
wherein R3 and R4 may represent mono-, or di-substitutions, or no substitution;
wherein R5 may represent mono-, di-, or tri-substitutions, or no substitution;
wherein R1 and R2 are independently selected from the group consisting of alkyl and cycloalkyl;
wherein R3, R4 and R5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof;
wherein any two adjacent substituents of R1, R2, R3, R4 and R5 are optionally joined to condense into a fused ring; and
wherein the dash lines show the connection points to osmium.
2. The compound of claim 1, wherein, for L2, Y1 and Y3 comprise C, and Y2 is N.
3. The compound of claim 1, wherein, for L2, Y1 and Y3 are N, and Y2 comprise C.
4. The compound of claim 1, wherein each R1 and R2 is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and partially or fully deuterated variants thereof.
5. The compound of claim 1, wherein each R1 and R2 is independently selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.
6. The compound of claim 1, wherein L1 and L2 are independently selected from ligands having Formula III:
Figure US20170250354A1-20170831-C00220
wherein each X1, X2, X3, X4, X5, X6, X7 and X8 independently comprises C or N.
7. The compound of claim 1, wherein each X1, X2, X3, X4, X5, X6, X7 and X8 comprises C.
8. The compound of claim 1, wherein ligand L1 is selected from the group consisting of:
Figure US20170250354A1-20170831-C00221
Figure US20170250354A1-20170831-C00222
Figure US20170250354A1-20170831-C00223
Figure US20170250354A1-20170831-C00224
Figure US20170250354A1-20170831-C00225
Figure US20170250354A1-20170831-C00226
Figure US20170250354A1-20170831-C00227
Figure US20170250354A1-20170831-C00228
Figure US20170250354A1-20170831-C00229
Figure US20170250354A1-20170831-C00230
Figure US20170250354A1-20170831-C00231
Figure US20170250354A1-20170831-C00232
Figure US20170250354A1-20170831-C00233
Figure US20170250354A1-20170831-C00234
Figure US20170250354A1-20170831-C00235
Figure US20170250354A1-20170831-C00236
9. The compound of claim 1, wherein R5 of L1 is different from R5 of L2.
10. The compound of claim 1, wherein, for L1, Y1, Y2 and Y3 comprise C, and, for L2, Y1 and Y3 comprises C and Y2 is N
11. The compound of claim 1, wherein, for L1, Y1, Y2 and Y3 comprise C, and, for L2, Y1 and Y3 are N, and Y2 comprises C.
12. The compound of claim 1, wherein for L1, Y1 and Y3 comprises C and Y2 is N, and, for L2, Y1 and Y3 are N, and Y2 comprises C.
13. A first device comprising a first organic light emitting device, the first organic light emitting device comprising:
an anode;
a cathode; and
an organic layer, disposed between the anode and the cathode, comprising a compound having the structure according Formula I

L1-Os-L2;
wherein L1 and L2 are different;
wherein L1 and L2 are independently selected from ligands having Formula II:
Figure US20170250354A1-20170831-C00237
wherein:
1) for L1, Y1, Y2 and Y3 comprise C and, for L2, either (i) Y1 and Y3 comprises C and Y2 is N, or (ii) Y1 and Y3 are N, and Y2 comprises C, or
2) for L1, Y1 and Y3 comprises C and Y2 is N, and, for L2, Y1 and Y3 are N, and Y2 comprises C;
wherein R3 and R4 may represent mono-, or di-substitutions, or no substitution;
wherein R5 may represent mono-, di-, or tri-substitutions, or no substitution;
wherein R1 and R2 are independently selected from the group consisting of alkyl and cycloalkyl;
wherein R3, R4 and R5 are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof,
wherein any two adjacent substituents of R1, R2, R3, R4 and R5 are optionally joined to condense into a fused ring; and
wherein the dash lines show the connection points to osmium.
14. The first device of claim 13, wherein the first device is a consumer product selected from the group consisting of light panels, flat panel displays, computer monitors, medical 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, 3-D displays, vehicles, large area walls, theater or stadium screens, and signs.
15. The first device of claim 13, wherein the first device is an organic light emitting device.
16. The first device of claim 13, wherein the organic layer is an emissive layer and the compound is an emissive dopant or a non-emissive dopant.
17. The first device of claim 13, wherein the organic layer further comprises a host material.
18. The first device of claim 17, wherein the host material comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan;
wherein any substituent in the host material is an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡CCnH2n+1, Ar1, Ar1—Ar2, and CnH2n—Ar1;
wherein n is from 1 to 10; and
wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
19. The first device of claim 17, wherein the host material comprises at least one chemical group selected from the group consisting of carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
20. The first device of claim 17, wherein the host material is selected from the group consisting of:
Figure US20170250354A1-20170831-C00238
Figure US20170250354A1-20170831-C00239
and combinations thereof.
US15/594,046 2013-07-25 2017-05-12 Organic electroluminescent materials and devices Abandoned US20170250354A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US15/594,046 US20170250354A1 (en) 2013-07-25 2017-05-12 Organic electroluminescent materials and devices
US16/784,609 US10930866B2 (en) 2013-07-25 2020-02-07 Organic electroluminescent materials and devices

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/950,591 US20150028290A1 (en) 2013-07-25 2013-07-25 Heteroleptic osmium complex and method of making the same
US15/594,046 US20170250354A1 (en) 2013-07-25 2017-05-12 Organic electroluminescent materials and devices

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US13/950,591 Continuation US20150028290A1 (en) 2013-07-25 2013-07-25 Heteroleptic osmium complex and method of making the same

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US16/784,609 Continuation US10930866B2 (en) 2013-07-25 2020-02-07 Organic electroluminescent materials and devices

Publications (1)

Publication Number Publication Date
US20170250354A1 true US20170250354A1 (en) 2017-08-31

Family

ID=51224767

Family Applications (3)

Application Number Title Priority Date Filing Date
US13/950,591 Abandoned US20150028290A1 (en) 2013-07-25 2013-07-25 Heteroleptic osmium complex and method of making the same
US15/594,046 Abandoned US20170250354A1 (en) 2013-07-25 2017-05-12 Organic electroluminescent materials and devices
US16/784,609 Active US10930866B2 (en) 2013-07-25 2020-02-07 Organic electroluminescent materials and devices

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US13/950,591 Abandoned US20150028290A1 (en) 2013-07-25 2013-07-25 Heteroleptic osmium complex and method of making the same

Family Applications After (1)

Application Number Title Priority Date Filing Date
US16/784,609 Active US10930866B2 (en) 2013-07-25 2020-02-07 Organic electroluminescent materials and devices

Country Status (4)

Country Link
US (3) US20150028290A1 (en)
EP (1) EP2830109A1 (en)
JP (1) JP2015024991A (en)
KR (2) KR20150013009A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150028290A1 (en) * 2013-07-25 2015-01-29 Universal Display Corporation Heteroleptic osmium complex and method of making the same
BR112021019077A2 (en) * 2019-03-27 2021-11-30 Kemin Ind Inc Methods for making one or more metal carboxylates and multiple metal carboxylates in a single reaction, and, metal carboxylate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090092854A1 (en) * 2007-10-04 2009-04-09 Entire Interest Complexes with tridentate ligands
US20110057559A1 (en) * 2007-12-28 2011-03-10 Universal Display Corporation Phosphorescent emitters and host materials with improved stability

Family Cites Families (147)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4769292A (en) 1987-03-02 1988-09-06 Eastman Kodak Company Electroluminescent device with modified thin film luminescent zone
GB8909011D0 (en) 1989-04-20 1989-06-07 Friend Richard H Electroluminescent devices
US5061569A (en) 1990-07-26 1991-10-29 Eastman Kodak Company Electroluminescent device with organic electroluminescent medium
EP0650955B1 (en) 1993-11-01 1998-08-19 Hodogaya Chemical Co., Ltd. Amine compound and electro-luminescence device comprising same
US5703436A (en) 1994-12-13 1997-12-30 The Trustees Of Princeton University Transparent contacts for organic devices
US5707745A (en) 1994-12-13 1998-01-13 The Trustees Of Princeton University Multicolor organic light emitting devices
US6939625B2 (en) 1996-06-25 2005-09-06 Nôrthwestern University Organic light-emitting diodes and methods for assembly and enhanced charge injection
US5844363A (en) 1997-01-23 1998-12-01 The Trustees Of Princeton Univ. Vacuum deposited, non-polymeric flexible organic light emitting devices
US5834893A (en) 1996-12-23 1998-11-10 The Trustees Of Princeton University High efficiency organic light emitting devices with light directing structures
US6091195A (en) 1997-02-03 2000-07-18 The Trustees Of Princeton University Displays having mesa pixel configuration
US6013982A (en) 1996-12-23 2000-01-11 The Trustees Of Princeton University Multicolor display devices
US6303238B1 (en) 1997-12-01 2001-10-16 The Trustees Of Princeton University OLEDs doped with phosphorescent compounds
US6337102B1 (en) 1997-11-17 2002-01-08 The Trustees Of Princeton University Low pressure vapor phase deposition of organic thin films
US6087196A (en) 1998-01-30 2000-07-11 The Trustees Of Princeton University Fabrication of organic semiconductor devices using ink jet printing
US6528187B1 (en) 1998-09-08 2003-03-04 Fuji Photo Film Co., Ltd. Material for luminescence element and luminescence element using the same
US6097147A (en) 1998-09-14 2000-08-01 The Trustees Of Princeton University Structure for high efficiency electroluminescent device
US6830828B2 (en) 1998-09-14 2004-12-14 The Trustees Of Princeton University Organometallic complexes as phosphorescent emitters in organic LEDs
US6294398B1 (en) 1999-11-23 2001-09-25 The Trustees Of Princeton University Method for patterning devices
US6458475B1 (en) 1999-11-24 2002-10-01 The Trustee Of Princeton University Organic light emitting diode having a blue phosphorescent molecule as an emitter
KR100377321B1 (en) 1999-12-31 2003-03-26 주식회사 엘지화학 Electronic device comprising organic compound having p-type semiconducting characteristics
US20020121638A1 (en) 2000-06-30 2002-09-05 Vladimir Grushin Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds
JP2002050860A (en) 2000-08-04 2002-02-15 Toray Eng Co Ltd Method and device for mounting
US6579630B2 (en) 2000-12-07 2003-06-17 Canon Kabushiki Kaisha Deuterated semiconducting organic compounds used for opto-electronic devices
JP3812730B2 (en) 2001-02-01 2006-08-23 富士写真フイルム株式会社 Transition metal complex and light emitting device
JP4307000B2 (en) 2001-03-08 2009-08-05 キヤノン株式会社 Metal coordination compound, electroluminescent element and display device
JP4310077B2 (en) 2001-06-19 2009-08-05 キヤノン株式会社 Metal coordination compound and organic light emitting device
DE60232415D1 (en) 2001-06-20 2009-07-02 Showa Denko Kk LIGHT-EMITTING MATERIAL AND ORGANIC LUMINAIRE DIODE
US7071615B2 (en) 2001-08-20 2006-07-04 Universal Display Corporation Transparent electrodes
US7250226B2 (en) 2001-08-31 2007-07-31 Nippon Hoso Kyokai Phosphorescent compound, a phosphorescent composition and an organic light-emitting device
US7431968B1 (en) 2001-09-04 2008-10-07 The Trustees Of Princeton University Process and apparatus for organic vapor jet deposition
US6835469B2 (en) 2001-10-17 2004-12-28 The University Of Southern California Phosphorescent compounds and devices comprising the same
US7166368B2 (en) 2001-11-07 2007-01-23 E. I. Du Pont De Nemours And Company Electroluminescent platinum compounds and devices made with such compounds
US6863997B2 (en) 2001-12-28 2005-03-08 The Trustees Of Princeton University White light emitting OLEDs from combined monomer and aggregate emission
KR100691543B1 (en) 2002-01-18 2007-03-09 주식회사 엘지화학 New material for transporting electron and organic electroluminescent display using the same
US20030230980A1 (en) 2002-06-18 2003-12-18 Forrest Stephen R Very low voltage, high efficiency phosphorescent oled in a p-i-n structure
US7189989B2 (en) 2002-08-22 2007-03-13 Fuji Photo Film Co., Ltd. Light emitting element
WO2004020549A1 (en) 2002-08-27 2004-03-11 Fujitsu Limited Organometallic complexes, organic el devices, and organic el displays
US6687266B1 (en) 2002-11-08 2004-02-03 Universal Display Corporation Organic light emitting materials and devices
JP4365199B2 (en) 2002-12-27 2009-11-18 富士フイルム株式会社 Organic electroluminescence device
JP4365196B2 (en) 2002-12-27 2009-11-18 富士フイルム株式会社 Organic electroluminescence device
WO2004085450A2 (en) 2003-03-24 2004-10-07 The University Of Southern California Phenyl-pyrazole complexes of ir
US7090928B2 (en) 2003-04-01 2006-08-15 The University Of Southern California Binuclear compounds
JP5318347B2 (en) 2003-04-15 2013-10-16 メルク パテント ゲーエムベーハー Mixture of matrix material and organic semiconductor capable of emitting light, use thereof, and electronic component comprising said mixture
US7029765B2 (en) 2003-04-22 2006-04-18 Universal Display Corporation Organic light emitting devices having reduced pixel shrinkage
WO2004107822A1 (en) 2003-05-29 2004-12-09 Nippon Steel Chemical Co., Ltd. Organic electroluminescent element
JP2005011610A (en) 2003-06-18 2005-01-13 Nippon Steel Chem Co Ltd Organic electroluminescent element
US20050025993A1 (en) 2003-07-25 2005-02-03 Thompson Mark E. Materials and structures for enhancing the performance of organic light emitting devices
TWI390006B (en) 2003-08-07 2013-03-21 Nippon Steel Chemical Co Organic EL materials with aluminum clamps
DE10338550A1 (en) 2003-08-19 2005-03-31 Basf Ag Transition metal complexes with carbene ligands as emitters for organic light-emitting diodes (OLEDs)
US20060269780A1 (en) 2003-09-25 2006-11-30 Takayuki Fukumatsu Organic electroluminescent device
JP4822687B2 (en) 2003-11-21 2011-11-24 富士フイルム株式会社 Organic electroluminescence device
US7332232B2 (en) 2004-02-03 2008-02-19 Universal Display Corporation OLEDs utilizing multidentate ligand systems
KR100834327B1 (en) 2004-03-11 2008-06-02 미쓰비시 가가꾸 가부시키가이샤 Composition for charge-transporting film and ion compound, charge-transporting film and organic electroluminescent device using same, and method for manufacturing organic electroluminescent device and method for producing charge-transporting film
TW200531592A (en) 2004-03-15 2005-09-16 Nippon Steel Chemical Co Organic electroluminescent device
JP4869565B2 (en) 2004-04-23 2012-02-08 富士フイルム株式会社 Organic electroluminescence device
US7279704B2 (en) 2004-05-18 2007-10-09 The University Of Southern California Complexes with tridentate ligands
US7534505B2 (en) 2004-05-18 2009-05-19 The University Of Southern California Organometallic compounds for use in electroluminescent devices
US7393599B2 (en) 2004-05-18 2008-07-01 The University Of Southern California Luminescent compounds with carbene ligands
US7445855B2 (en) 2004-05-18 2008-11-04 The University Of Southern California Cationic metal-carbene complexes
US7154114B2 (en) 2004-05-18 2006-12-26 Universal Display Corporation Cyclometallated iridium carbene complexes for use as hosts
US7491823B2 (en) 2004-05-18 2009-02-17 The University Of Southern California Luminescent compounds with carbene ligands
WO2005123873A1 (en) 2004-06-17 2005-12-29 Konica Minolta Holdings, Inc. Organic electroluminescent device material, organic electroluminescent device, display and illuminating device
JP5000496B2 (en) 2004-06-28 2012-08-15 チバ ホールディング インコーポレーテッド Electroluminescent metal complexes of triazole and benzotriazole
US20060008670A1 (en) 2004-07-06 2006-01-12 Chun Lin Organic light emitting materials and devices
JP4858169B2 (en) 2004-07-23 2012-01-18 コニカミノルタホールディングス株式会社 Organic electroluminescence device
DE102004057072A1 (en) 2004-11-25 2006-06-01 Basf Ag Use of Transition Metal Carbene Complexes in Organic Light Emitting Diodes (OLEDs)
US8362463B2 (en) 2004-12-30 2013-01-29 E. I. Du Pont De Nemours And Company Organometallic complexes
WO2006082742A1 (en) 2005-02-04 2006-08-10 Konica Minolta Holdings, Inc. Organic electroluminescent device material, organic electroluminescent device, display and illuminating device
KR100803125B1 (en) 2005-03-08 2008-02-14 엘지전자 주식회사 Red phosphorescent compounds and organic electroluminescence devices using the same
JP5125502B2 (en) 2005-03-16 2013-01-23 コニカミノルタホールディングス株式会社 Organic electroluminescence element material, organic electroluminescence element
DE102005014284A1 (en) 2005-03-24 2006-09-28 Basf Ag Use of compounds containing aromatic or heteroaromatic rings containing groups via carbonyl groups as matrix materials in organic light-emitting diodes
WO2006103874A1 (en) 2005-03-29 2006-10-05 Konica Minolta Holdings, Inc. Organic electroluminescent device material, organic electroluminescent device, display and illuminating device
GB2439030B (en) 2005-04-18 2011-03-02 Konica Minolta Holdings Inc Organic electroluminescent device, display and illuminating device
US7807275B2 (en) 2005-04-21 2010-10-05 Universal Display Corporation Non-blocked phosphorescent OLEDs
JP4533796B2 (en) 2005-05-06 2010-09-01 富士フイルム株式会社 Organic electroluminescence device
US9051344B2 (en) 2005-05-06 2015-06-09 Universal Display Corporation Stability OLED materials and devices
US8007927B2 (en) 2007-12-28 2011-08-30 Universal Display Corporation Dibenzothiophene-containing materials in phosphorescent light emitting diodes
CN101203583A (en) 2005-05-31 2008-06-18 通用显示公司 Triphenylene hosts in phosphorescent light emitting diodes
JP4976288B2 (en) 2005-06-07 2012-07-18 新日鐵化学株式会社 Organometallic complex and organic electroluminescence device using the same
JP5324217B2 (en) 2005-06-27 2013-10-23 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Conductive polymer composition
WO2007004380A1 (en) 2005-07-01 2007-01-11 Konica Minolta Holdings, Inc. Organic electroluminescent element material, organic electroluminescent element, display device, and lighting equipment
WO2007028417A1 (en) 2005-09-07 2007-03-15 Technische Universität Braunschweig Triplett emitter having condensed five-membered rings
JP4887731B2 (en) 2005-10-26 2012-02-29 コニカミノルタホールディングス株式会社 Organic electroluminescence element, display device and lighting device
US20090295276A1 (en) 2005-12-01 2009-12-03 Tohru Asari Organic Electroluminescent Device
CN101321755B (en) 2005-12-01 2012-04-18 新日铁化学株式会社 Compound for organic electroluminescent element and organic electroluminescent element
US8142909B2 (en) 2006-02-10 2012-03-27 Universal Display Corporation Blue phosphorescent imidazophenanthridine materials
KR20210130847A (en) 2006-02-10 2021-11-01 유니버셜 디스플레이 코포레이션 METAL COMPLEXES OF CYCLOMETALLATED IMIDAZO[1,2-f]PHENANTHRIDINE AND DIIMIDAZO[1,2-A:1',2'-C]QUINAZOLINE LIGANDS AND ISOELECTRONIC AND BENZANNULATED ANALOGS THEREOF
JP4823730B2 (en) 2006-03-20 2011-11-24 新日鐵化学株式会社 Luminescent layer compound and organic electroluminescent device
ATE550342T1 (en) 2006-04-05 2012-04-15 Basf Se HETEROLEPTIC TRANSITION METAL-CARBEN COMPLEXES AND THEIR USE IN ORGANIC LIGHT-LIGHT DIODES (OLEDS)
KR101551591B1 (en) 2006-04-26 2015-09-08 이데미쓰 고산 가부시키가이샤 Aromatic amine derivative, and organic electroluminescence element using the same
JP5432523B2 (en) 2006-05-11 2014-03-05 出光興産株式会社 Organic electroluminescence device
KR20090016684A (en) 2006-06-02 2009-02-17 이데미쓰 고산 가부시키가이샤 Material for organic electroluminescence element, and organic electroluminescence element using the material
DE102006035018B4 (en) 2006-07-28 2009-07-23 Novaled Ag Oxazole triplet emitter for OLED applications
WO2008023550A1 (en) 2006-08-23 2008-02-28 Idemitsu Kosan Co., Ltd. Aromatic amine derivative and organic electroluminescent device employing the same
JP5589251B2 (en) 2006-09-21 2014-09-17 コニカミノルタ株式会社 Organic electroluminescence element material
US7968146B2 (en) 2006-11-01 2011-06-28 The Trustees Of Princeton University Hybrid layers for use in coatings on electronic devices or other articles
CN101511834B (en) 2006-11-09 2013-03-27 新日铁化学株式会社 Compound for organic electroluminescent device and organic electroluminescent device
KR20120135325A (en) 2006-11-24 2012-12-12 이데미쓰 고산 가부시키가이샤 Aromatic amine derivative and organic electroluminescent element using the same
US8119255B2 (en) 2006-12-08 2012-02-21 Universal Display Corporation Cross-linkable iridium complexes and organic light-emitting devices using the same
EP2112994B1 (en) 2007-02-23 2011-01-26 Basf Se Electroluminescent metal complexes with benzotriazoles
CN101687893B (en) 2007-04-26 2014-01-22 巴斯夫欧洲公司 Silanes containing phenothiazine-S-oxide or phenothiazine-S,S-dioxide groups and the use thereof in OLEDs
US8440826B2 (en) 2007-06-22 2013-05-14 Basf Se Light emitting Cu (I) complexes
CN101878552B (en) 2007-07-05 2015-07-15 巴斯夫欧洲公司 Organic light-emitting diodes containing carbene transition metal complex emitters and at least one compound selected from disilylcarbazoles, disilyldibenzofurans, disilyldibenzothiophenes, disilyldibenzophospholes, disilyldibenzothiophene s-oxides a
US20090045731A1 (en) 2007-07-07 2009-02-19 Idemitsu Kosan Co., Ltd. Organic electroluminescence device and material for organic electroluminescence device
US8779655B2 (en) 2007-07-07 2014-07-15 Idemitsu Kosan Co., Ltd. Organic electroluminescence device and material for organic electroluminescence device
TW200909560A (en) 2007-07-07 2009-03-01 Idemitsu Kosan Co Organic electroluminescence device and material for organic electroluminescence devcie
US8034256B2 (en) 2007-07-07 2011-10-11 Idemitsu Kosan Co., Ltd. Naphthalene derivative, material for organic electroluminescence device, and organic electroluminescence device using the same
KR20100031723A (en) 2007-07-07 2010-03-24 이데미쓰 고산 가부시키가이샤 Chrysene derivative and organic electroluminescent device using the same
EP2166584B1 (en) 2007-07-10 2016-06-08 Idemitsu Kosan Co., Ltd. Material for organic electroluminescence element, and organic electroluminescence element prepared by using the material
US8080658B2 (en) 2007-07-10 2011-12-20 Idemitsu Kosan Co., Ltd. Material for organic electroluminescent element and organic electroluminescent element employing the same
EP2173811A1 (en) 2007-07-27 2010-04-14 E. I. du Pont de Nemours and Company Aqueous dispersions of electrically conducting polymers containing inorganic nanoparticles
KR20160086983A (en) * 2007-08-08 2016-07-20 유니버셜 디스플레이 코포레이션 Benzo-fused thiophene or benzo-fused furan compounds comprising a triphenylene group
JP2009040728A (en) 2007-08-09 2009-02-26 Canon Inc Organometallic complex and organic light-emitting element using the same
US8067100B2 (en) * 2007-10-04 2011-11-29 Universal Display Corporation Complexes with tridentate ligands
ATE519770T1 (en) 2007-10-17 2011-08-15 Basf Se TRANSITION METAL COMPLEXES WITH BRIDGED CARBENE LIGANDS AND THEIR USE IN OLEDS
US20090101870A1 (en) 2007-10-22 2009-04-23 E. I. Du Pont De Nemours And Company Electron transport bi-layers and devices made with such bi-layers
US7914908B2 (en) 2007-11-02 2011-03-29 Global Oled Technology Llc Organic electroluminescent device having an azatriphenylene derivative
DE102007053771A1 (en) 2007-11-12 2009-05-14 Merck Patent Gmbh Organic electroluminescent devices
EP2216313B1 (en) 2007-11-15 2013-02-20 Idemitsu Kosan Co., Ltd. Benzochrysene derivative and organic electroluminescent device using the same
JP5270571B2 (en) 2007-11-22 2013-08-21 出光興産株式会社 Organic EL device
JP5390396B2 (en) 2007-11-22 2014-01-15 出光興産株式会社 Organic EL device and organic EL material-containing solution
WO2009073245A1 (en) 2007-12-06 2009-06-11 Universal Display Corporation Light-emitting organometallic complexes
US8221905B2 (en) 2007-12-28 2012-07-17 Universal Display Corporation Carbazole-containing materials in phosphorescent light emitting diodes
KR101812441B1 (en) 2008-02-12 2017-12-26 유디씨 아일랜드 리미티드 Electroluminescent metal complexes with dibenzo[f,h]quinoxalines
US8563737B2 (en) * 2011-02-23 2013-10-22 Universal Display Corporation Methods of making bis-tridentate carbene complexes of ruthenium and osmium
CN115448957A (en) * 2011-02-23 2022-12-09 通用显示公司 Novel tetradentate platinum complexes
US9005772B2 (en) * 2011-02-23 2015-04-14 Universal Display Corporation Thioazole and oxazole carbene metal complexes as phosphorescent OLED materials
US8883322B2 (en) * 2011-03-08 2014-11-11 Universal Display Corporation Pyridyl carbene phosphorescent emitters
JP2014523410A (en) * 2011-06-08 2014-09-11 ユニバーサル ディスプレイ コーポレイション Heteroleptic iridium carbene complex and light emitting device using the same
US9783564B2 (en) * 2011-07-25 2017-10-10 Universal Display Corporation Organic electroluminescent materials and devices
US9312505B2 (en) * 2012-09-25 2016-04-12 Universal Display Corporation Organic electroluminescent materials and devices
US10069090B2 (en) * 2012-11-20 2018-09-04 Universal Display Corporation Organic electroluminescent materials and devices
US20150028290A1 (en) * 2013-07-25 2015-01-29 Universal Display Corporation Heteroleptic osmium complex and method of making the same
US9306179B2 (en) * 2013-11-08 2016-04-05 Universal Display Corporation Organic electroluminescent materials and devices
US9978961B2 (en) * 2014-01-08 2018-05-22 Universal Display Corporation Organic electroluminescent materials and devices
US9935277B2 (en) * 2014-01-30 2018-04-03 Universal Display Corporation Organic electroluminescent materials and devices
US9590194B2 (en) * 2014-02-14 2017-03-07 Universal Display Corporation Organic electroluminescent materials and devices
US9590195B2 (en) * 2014-02-28 2017-03-07 Universal Display Corporation Organic electroluminescent materials and devices
US9748504B2 (en) * 2014-03-25 2017-08-29 Universal Display Corporation Organic electroluminescent materials and devices
CN106463619B (en) * 2014-05-08 2020-07-07 环球展览公司 Stabilized imidazophenanthridine materials
US10868261B2 (en) * 2014-11-10 2020-12-15 Universal Display Corporation Organic electroluminescent materials and devices
US9882151B2 (en) * 2014-11-14 2018-01-30 Universal Display Corporation Organic electroluminescent materials and devices
US9450195B2 (en) * 2014-12-17 2016-09-20 Universal Display Corporation Organic electroluminescent materials and devices
US10418569B2 (en) * 2015-01-25 2019-09-17 Universal Display Corporation Organic electroluminescent materials and devices
US9929361B2 (en) * 2015-02-16 2018-03-27 Universal Display Corporation Organic electroluminescent materials and devices
US20180370999A1 (en) * 2017-06-23 2018-12-27 Universal Display Corporation Organic electroluminescent materials and devices
US11271177B2 (en) * 2018-01-11 2022-03-08 Universal Display Corporation Organic electroluminescent materials and devices

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090092854A1 (en) * 2007-10-04 2009-04-09 Entire Interest Complexes with tridentate ligands
US20110057559A1 (en) * 2007-12-28 2011-03-10 Universal Display Corporation Phosphorescent emitters and host materials with improved stability

Also Published As

Publication number Publication date
US20150028290A1 (en) 2015-01-29
KR102312243B1 (en) 2021-10-13
US10930866B2 (en) 2021-02-23
KR20200130669A (en) 2020-11-19
US20200176694A1 (en) 2020-06-04
EP2830109A1 (en) 2015-01-28
JP2015024991A (en) 2015-02-05
KR20150013009A (en) 2015-02-04

Similar Documents

Publication Publication Date Title
US11943999B2 (en) Organic electroluminescent materials and devices
US11917902B2 (en) Organic electroluminescent materials and devices
US11145831B2 (en) Osmium(IV) complexes for OLED materials
US8987451B2 (en) Synthesis of cyclometallated platinum(II) complexes
US9231218B2 (en) Phosphorescent emitters containing dibenzo[1,4]azaborinine structure
US9663544B2 (en) Organic electroluminescent materials and devices
US10033000B2 (en) Organic electroluminescent materials and devices
US9190621B2 (en) Materials for organic light emitting diode
US9670404B2 (en) Organic electroluminescent materials and devices
US20150069334A1 (en) Iridium/platinum metal complex
US10388890B2 (en) Organic electroluminescent heterocyclic carbene metal complexes and devices containing the same
US20140027733A1 (en) Transition metal complexes containing substituted imidazole carbene as ligands and their application in oleds
US9847497B2 (en) Organic electroluminescent materials and devices
US9978958B2 (en) Phosphorescent emitters with phenylimidazole ligands
US10199582B2 (en) Organic electroluminescent materials and devices
US20160133859A1 (en) Organic electroluminescent materials and devices
US9871214B2 (en) Organic electroluminescent materials and devices
US9306179B2 (en) Organic electroluminescent materials and devices
US9748503B2 (en) Organic electroluminescent materials and devices
US10930866B2 (en) Organic electroluminescent materials and devices
US9997712B2 (en) Organic electroluminescent materials and devices

Legal Events

Date Code Title Description
AS Assignment

Owner name: UNIVERSAL DISPLAY CORPORATION, NEW JERSEY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:XIA, CHUANJUN;TSAI, JUI-YI;ARMENDARIZ, BEATRIZ EGUILLOR;AND OTHERS;SIGNING DATES FROM 20130725 TO 20130729;REEL/FRAME:042437/0333

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION