WO2015175130A1 - Composé luminescent bleu et ses diastéréoisomères - Google Patents

Composé luminescent bleu et ses diastéréoisomères Download PDF

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WO2015175130A1
WO2015175130A1 PCT/US2015/025720 US2015025720W WO2015175130A1 WO 2015175130 A1 WO2015175130 A1 WO 2015175130A1 US 2015025720 W US2015025720 W US 2015025720W WO 2015175130 A1 WO2015175130 A1 WO 2015175130A1
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composition
deuterated
enantiomers
aryl
formula
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Jerald Feldman
Kyung-Ho Park
Ying Wang
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E. I. Du Pont De Nemours And Company
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • 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
    • 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
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three 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
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • This disclosure relates in general to compositions of diastereomeric pairs of enantiomers of blue luminescent compounds and their use in electronic devices.
  • Organic electronic devices that emit light, such as light-emitting diodes that make up displays, are present in many different kinds of electronic equipment.
  • an organic active layer is sandwiched between two electrical contact layers. At least one of the electrical contact layers is light-transmitting so that light can pass through the electrical contact layer.
  • the organic active layer emits light through the light-transmitting electrical contact layer upon application of electricity across the electrical contact layers.
  • organic electroluminescent compounds As the active component in light-emitting diodes. Simple organic molecules, such as anthracene, thiadiazole derivatives, and coumarin derivatives are known to show electroluminescence. Metal complexes, particularly iridium and platinum complexes are also known to show electroluminescence. In some cases these small molecule compounds are present as a dopant in a host material to improve processing and/or electronic properties.
  • composition capable of being separated into n diastereomeric pairs of enantiomers, the composition having Formula I Formula I
  • Ar' is selected from the group consisting of aryl and deuterated aryl
  • R 1 is selected from the group consisting of H, D, alkyl, silyl, aryl, and deuterated analogs thereof;
  • R 2 is different from R 1 and is selected from the group consisting of
  • R 1 and R 2 are H or D
  • R 3 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, silyl, aryl, and deuterated analogs thereof;
  • a is an integer from 0-3;
  • b is an integer from 0-4.
  • composition consisting essentially of n diastereomeric pairs of enantiomers of Formula I, where n is 1 , 2, or 3.
  • an organic electronic device comprising a first electrical contact, a second electrical contact and a photoactive layer therebetween, the photoactive layer comprising the composition of Formula I.
  • an organic electronic device comprising a first electrical contact, a second electrical contact and a photoactive layer therebetween, the photoactive layer comprising n diastereomeric pairs of enantiomers having Formula I.
  • FIG. 1 includes an illustration of an organic light-emitting device.
  • FIG. 2 includes another illustration of an organic light-emitting device.
  • alkyl is intended to mean a group derived from an aliphatic hydrocarbon and includes a linear, a branched, or a cyclic group. In some embodiments, an alkyl has from 1 -20 carbon atoms.
  • aromatic compound is intended to mean an organic compound comprising at least one unsaturated cyclic group having delocalized pi electrons.
  • aryl is intended to mean a group derived from an aromatic hydrocarbon having one point of attachment. The term includes groups which have a single ring and those which have multiple rings which can be joined by a single bond or fused together. The term is intended to include both hydrocarbon aryls, having only carbon in the ring structure, and heteroaryls.
  • alkylaryl is intended to mean an aryl group having one or more alkyl substituents. In some embodiments, a
  • hydrocarbon aryl has 6-60 ring carbons.
  • a heteroaryl has 3-60 ring carbons.
  • charge transport when referring to a layer, material, member, or structure is intended to mean such layer, material, member, or structure facilitates migration of such charge through the thickness of such layer, material, member, or structure with relative efficiency and small loss of charge.
  • Hole transport materials facilitate positive charge; electron transport materials facilitate negative charge.
  • light-emitting materials may also have some charge transport properties, the term "charge transport layer, material, member, or structure” is not intended to include a layer, material, member, or structure whose primary function is light emission.
  • chiral refers to a compound or group which is not superimposable on its mirror image.
  • a compound that is chiral is usually obtained as a mixture of two "enantiomers” as defined below.
  • atropisomer refers to a specific kind of chiral compound that is chiral as the result of hindered internal bond rotation. Atropisomerism is reviewed in the following reference: Bringmann, G.; Price Mortimer, A. J.; Keller, P. A.; Gresser, M. J.; Garner, J.; Breuning, M. Angew. Chem., Int. Ed. 2005, 44, 5384.
  • a compound that has a chiral center as the result of
  • deuterated is intended to mean that at least one hydrogen has been replaced by deuterium, abbreviated herein as "D".
  • deuterated analog refers to a structural analog of a compound or group in which one or more available hydrogens have been replaced with deuterium. In a deuterated compound or deuterated analog, the deuterium is present in at least 100 times the natural abundance level.
  • stereoisomers that are not enantiomers.
  • Diastereomerism occurs when two or more stereoisomers of a compound have different configurations at one or more (but not all) of the equivalent related stereocenters and are not mirror images of each other.
  • diastereomeric pair of enantiomers refers to a set of two stereoisomers, where the stereoisomers in the set are mirror images and where the set is not a mirror image of any other sets of two stereoisomers.
  • dopant is intended to mean a material, within a layer including a host material, that changes the electronic characteristic(s) or the targeted wavelength(s) of radiation emission, reception, or filtering of the layer compared to the electronic characteristic(s) or the wavelength(s) of radiation emission, reception, or filtering of the layer in the absence of such material.
  • hetero indicates that one or more carbon atoms have been replaced with a different atom.
  • the different atom is N, O, or S.
  • host material is intended to mean a material, usually in the form of a layer, to which a dopant may be added.
  • the host material may or may not have electronic characteristic(s) or the ability to emit, receive, or filter radiation.
  • layer is used interchangeably with the term “film” and refers to a coating covering a desired area.
  • the term is not limited by size.
  • the area can be as large as an entire device or as small as a specific functional area such as the actual visual display, or as small as a single sub-pixel.
  • Layers and films can be formed by any conventional deposition technique, including vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer.
  • Continuous deposition techniques include but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot-die coating, spray coating, and continuous nozzle coating or printing.
  • Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing.
  • luminescent material and “emitter” are intended to mean a material that emits light when activated by an applied voltage (such as in a light-emitting diode or light-emitting electrochemical cell).
  • organic electronic device or sometimes just “electronic device” is intended to mean a device including one or more organic semiconductor layers or materials.
  • photoactive refers to a material or layer that emits light when activated by an applied voltage (such as in a light emitting diode or chemical cell), that emits light after the absorption of photons (such as in down-converting phosphor devices), or that responds to radiant energy and generates a signal with or without an applied bias voltage (such as in a photodetector or a photovoltaic cell).
  • an applied voltage such as in a light emitting diode or chemical cell
  • photons such as in down-converting phosphor devices
  • an applied bias voltage such as in a photodetector or a photovoltaic cell
  • sil refers to the group R 3 Si-, where R is H, D, C1 -20 alkyl, fluoroalkyl, or aryl.
  • stereoisomers refers to isomeric molecules that have the same molecular formula and sequence of bonded atoms, but that differ only in the three-dimensional orientations of their atoms in space. One stereoisomer cannot be superimposed on another.
  • the ligands in the composition of Formula I have the general structure shown below, where R 3 is not shown:
  • the two structures are non-superimposable mirror images.
  • the two enantiomers can be described as defining left-handed (“ ⁇ ") or right- handed (“ ⁇ ") helices (see S. Herrero and M. A. Uson J. Chem. Ed. 1995, 72, 1065 for the naming convention).
  • stereoisomers when three identical chiral bidentate ligands are complexed to an octahedral metal center. That is because the ligand is a racemate (a 50/50 mixture of enantiomers) and the Ir center is a racemate as well (" ⁇ " or " ⁇ ” as shown above). These stereoisomers are actually four diastereomeric pairs of enantiomers.
  • the lrl_ 3 complex as formed, can be separated into four physically different diastereomeric pairs of
  • ⁇ and ⁇ refer to the stereochemistry of the iridium center
  • M and P refer to stereochemistry of the ligands It is possible to distinguish between MMM/PPP and MPP/PMM
  • the relative configuration at Ir can be determined by x-ray crystallography. In some cases it is only known whether the complex is an MMM/PPP or MPP/PMM diastereomeric pair of enantiomers. In those instances where x-ray quality crystals can be obtained, the relative configuration at Ir can be
  • the stereochemistry of the complexed ligand is characterized according to the rules described in Bringmann, et al.
  • the assignment of the absolute configuration depends on the relative priority of the substituents that are attached to the two aromatic groups that are connected by the rotationally restricted bond. For example, in the two atropisomers below, Ph > iPr and Ar' > Phenyl.
  • Application of the rules in Bringmann et al. leads to the atropisomers being designated as shown.
  • compositions capable of being separated into diastereomeric pairs of enantiomers the composition having Formula I.
  • compositions consist essentially of n diastereomeric pairs of enantiomers, where n is 1 , 2, or 3. While many iridium complexes have eight stereoisomeric forms, as discussed above, not all are capable of being separated into the
  • complexes of Formula I can be separated into diastereomeric pairs of enantiomers.
  • a mixture of n diastereomeric pairs of enantiomers can be isolated, where n is 1 , 2, or 3.
  • a mixture of two diastereomeric pairs of enantiomers can be isolated. In some embodiments, a single diastereomeric pair of enantiomers can be isolated.
  • composition consisting essentially of n diastereomeric pairs of enantiomers having Formula I, where n is 1 or 2. By this it is meant that there are one or two diastereomeric pairs of enantiomers and no other stereoisomers of the composition are present.
  • Ar' is selected from the group consisting of aryl and deuterated aryl
  • R 1 is selected from the group consisting of H, D, alkyl, silyl, aryl, and deuterated analogs thereof;
  • R 2 is different from R 1 and is selected from the group consisting of H, D, alkyl, silyl, aryl, and deuterated analogs thereof, with the proviso that no more than one of R 1 and R 2 is H or D;
  • R 3 is the same or different at each occurrence and is selected from the group consisting of D, alkyl, silyl, aryl, and deuterated analogs thereof; a is an integer from 0-3; and
  • b is an integer from 0-4.
  • the composition consists essentially of one diastereomeric pair of enantiomers.
  • the composition consists essentially of two diastereomeric pairs of enantiomers.
  • the two pairs have the same molecular formula and sequence of atoms and differ only in the three- dimensional orientation of their atoms.
  • the two pairs are not mirror images of each other.
  • the composition consists essentially of three diastereomeric pairs of enantiomers.
  • the three pairs have the same molecular formula and sequence of atoms and differ only in the three- dimensional orientation of their atoms. None of the three pairs is a mirror image of another of the three pairs.
  • composition of Formula I is deuterated.
  • the composition of Formula I is at least 10% deuterated.
  • % deuterated or “% deuteration” is meant the ratio of deuterons to the total of hydrogens plus deuterons, expressed as a percentage.
  • the deuteriums may be on the same or different groups.
  • the diastereomeric pair of enantiomers of Formula I is at least 25% deuterated; in some embodiments, at least 50% deuterated; in some embodiments, at least 75% deuterated; in some embodiments, at least 90% deuterated.
  • Ar' is selected from the group consisting of phenyl, biphenyl, naphthyl, substituted derivatives thereof, and deuterated analogs thereof.
  • substituents are selected from the group consisting of phenyl, 1 -napthyl, 1 -naphthyl, C1 -10 alkyl, C3-12 silyl, and deuterated analogs thereof.
  • Ar' has Formula II
  • R 4 is selected from the group consisting of alkyl, silyl, aryl, and
  • * indicates the point of attachment to the triazine ring of the ligand.
  • R 4 is selected from the group consisting of phenyl, C1 -10 alkyl, C3-12 silyl, and deuterated analogs thereof.
  • R 1 is selected from H and D.
  • R 1 is an unsubstituted alkyl or unsubstituted deuterated alkyl having 1 -6 carbons.
  • R 1 is an unsubstituted alkyl or unsubstituted deuterated alkyl having 1 -3 carbons.
  • R 1 is a silyl or deuterated silyl having 3-6 carbons.
  • R 1 is a C6-12 aryl or C6-12 deuterated aryl.
  • R 1 is phenyl or deuterated phenyl.
  • R 2 is selected from H and D.
  • R 2 is an unsubstituted alkyl or unsubstituted deuterated alkyl having 1 -6 carbons.
  • R 2 is an unsubstituted alkyl or unsubstituted deuterated alkyl having 1 -3 carbons.
  • R 2 is a silyl or deuterated silyl having 3-6 carbons.
  • R 2 is a C6-12 aryl or C6-12 deuterated aryl. In some embodiments, R 2 is phenyl or deuterated phenyl.
  • a 0.
  • a 1 .
  • a > 0 and R 3 is an alkyl or deuterated alkyl having 1 -6 carbons.
  • a > 0 and R 3 is a silyl or deuterated silyl having 3-6 carbons. In some embodiments, a > 0 and R 3 is a hydrocarbon aryl or deuterated hydrocarbon aryl having 6-12 ring carbons.
  • a > 0 and R 3 is an alkylaryl or deuterated alkylaryl having 6-20 carbons.
  • b 0.
  • b 1 .
  • b 2.
  • R 3 is an alkyl or deuterated alkyl having 1 -6 carbons.
  • b > 0 and R 3 is a silyl or deuterated silyl having 3-6 carbons.
  • R 3 is a hydrocarbon aryl or deuterated hydrocarbon aryl having 6-12 ring carbons.
  • R 3 is an alkylaryl or deuterated alkylaryl having 6-20 carbons.
  • any of the above embodiments can be combined with one or more of the other embodiments, so long as they are not mutually exclusive and with the proviso that no more than one of R 1 and R 2 is H or D, and R 1 ⁇ R 2 .
  • R 1 is an alkyl or deuterated alkyl having 3-20 carbons
  • R 2 is phenyl or deuterated phenyl
  • the composition consists essentially of one diastereomeric pair of enantiomers.
  • the same is true for the other non-mutually-exclusive embodiments discussed above. The skilled person would understand which embodiments were mutually exclusive and would thus readily be able to determine the combinations of embodiments that are contemplated by the present application.
  • the diastereomeric pair of enantiomers is intended to refer to n diastereomeric pairs of enantiomers, where n is 1 , 2, or 3.
  • the composition having Formula I is useful as an emissive material in electroluminescent or photoluminescent applications. In some embodiments, the composition having Formula I is capable of blue electroluminescence. The composition can be used alone or as a dopant in a host material.
  • compositions having Formula I are soluble in many commonly used organic solvents. Solutions of these compounds can be used for liquid deposition using techniques such as discussed above.
  • the compositions have an EL peak in the range of 445-490 nm.
  • the compounds used in devices result in color coordinates of x ⁇ 0.25 and y ⁇ 0.5, according to the 1931 CLE.
  • compositions having Formula I can provide advantages in electronic devices.
  • compositions having Formula I is used in light-emitting devices.
  • devices made with n diastereomeric pairs of enantiomers having Formula I have improved efficiencies and lifetimes. This is advantageous for reducing energy consumption in all types of devices, and particularly for lighting
  • devices made with n diastereomeric pairs of enantiomers have improved color.
  • the composition having Formula I is used as a down-converting phosphor in devices.
  • n diastereomeric pairs of enantiomers have improved efficiency and/or color.
  • compositions having Formula I exhibits biological activity.
  • one or more diastereomeric pairs of enantiomers can be more active than others.
  • diastereomeric pair of enantiomers can be more effective than others.
  • compositions having Formula I provides utility as a singlet oxygen photosensitizer or scavenger.
  • one or more diastereomeric pair of enantiomers can be more effective than others.
  • Examples of compositions having Formula I from which the diastereomenc pairs of enantiomers can be separated include, but are not limited to, those shown below. As discussed above, the diastereomeric pairs of enantiomers are classified as follows:
  • compositions B1 -B9 are understood to contain all of these possible diastereomers, which may or may not be separated prior to their incorporation into a luminescent device.
  • composition B5 Composition B6
  • the ligands for the compositions having Formula I described herein can be synthesized by a variety of procedures that have precedent in the literature. The exact procedure chosen will depend on a variety of factors, including availability of starting materials and reaction yield.
  • a diaryl 1 ,3,4-oxadiazole is prepared from a carboxylic acid and an acyl hydrazide (Dickson, H. D.; Li, C. Tet. Lett. 2009, 50, 6435).
  • the 1 ,3,4-oxadiazole is then allowed to react with an aniline in the presence of aluminum chloride to afford the desired 4H- 1 ,2,4-triazole (Chiriac, C. I. et al., Rev. Roum. Chim. 2010, 55, 175).
  • HATU 2 ⁇ (7 ⁇ Aza-1 H- Benzo riazole -1 -yi)-1 ,1 ,3,3- tetramethyluronium hexafluorophosphate
  • DIEA diisopropy!ethy!amine
  • Burgess Reagent methyl N- (triethylammoniumsulfonyl)carbamate
  • THF tetrahydrofuran
  • NMP 1 -methyl-2-pyrollidinone
  • 2-phenyl-1 ,3,4-oxadiazole is allowed to react with an aniline, affording a diaryl-substituted triazole (Korotikh, N.I. et al. Chemistry of Heterocyclic Compounds 2005, 41, 866).
  • the triazole is then allowed to react with N-bromosuccinimide affording a brominated 1 ,2,4- triazole, which then undergoes Suzuki coupling to afford a triaryl- substituted 4H-1 ,2,4-triazole.
  • An example of this method is shown below:
  • the Huisgen rearrangement reaction is yet another method that was used to prepare sterically hindered 4H-1 ,2,4-triazoles (Kaim, L. E.; Grimaud, L; Patil, P. Org. Lett. 2011 , 13, 1261 .).
  • the rearrangement takes advantage of the fast kinetics of an intramolecular cyclization driven by generation of N 2 to form bonds between bulky groups.
  • the synthetic sequence is summarized below. It is modular and convergent, allowing for flexibility in tuning the substituents on the triazole core.
  • the starting materials for the Huisgen rearrangement can be prepared from the readily available isonitrile and 5-phenyl-1 H-tetrazole.
  • the tetrazolyl imidoyl bromide undergoes rearrangement to from 3-bromo- 1 ,2,4-triazole.
  • the last step of the ligand synthesis is the Suzuki-Miyaura cross-coupling reaction.
  • compositions having Formula I were prepared by the reaction of commercially available lr(acetylacetonate)3 with excess ligand at elevated temperatures. This reaction typically results in cyclometallation of three equivalents of ligand onto iridium and formation of three equivalents of acetylacetone.
  • cyclometallated ligand can be isolated and purified by chromatography and/or recrystallization.
  • the diastereomeric pairs of enantiomers can be separated by chromatographic methods, such as flash chromatography or high performance liquid chromatography.
  • the structure of the diastereomeric pair of enantiomers can be determined by NMR and x-ray crystallography, as discussed above.
  • Organic electronic devices that may benefit from having one or more layers comprising the diastereomeric pairs of enantiomers having Formula I described herein include, but are not limited to, (1 ) devices that convert electrical energy into radiation (e.g., a light-emitting diode, light emitting diode display, lighting device, luminaire, or diode laser); (2) devices that detect signals through electronics processes (e.g.,
  • photodetectors photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes, IR detectors, biosensors
  • devices that convert radiation into electrical energy e.g., a photovoltaic device or solar cell
  • devices that convert light of one wavelength to light of a longer wavelength e.g., a down-converting phosphor device
  • devices that include one or more electronic components that include one or more organic semi-conductor layers e.g., a transistor or diode.
  • the device 100 has a first electrical contact layer, an anode layer 1 10 and a second electrical contact layer, a cathode layer 160, and a photoactive layer 140 between them.
  • Adjacent to the anode is a hole injection layer 120.
  • Adjacent to the hole injection layer is a hole transport layer 130, comprising hole transport material.
  • Adjacent to the cathode may be an electron transport layer 150, comprising an electron transport material.
  • devices may use one or more additional hole injection or hole transport layers (not shown) next to the anode 1 10 and/or one or more additional electron injection or electron transport layers (not shown) next to the cathode 160.
  • devices may have an anti-quenching layer (not shown) between the photoactive layer 140 and the electron transport layer 150.
  • Layers 120 through 150, and any additional layers between them, are individually and collectively referred to as the active layers.
  • the photoactive layer is pixellated, as shown in FIG. 2.
  • layer 140 is divided into pixel or subpixel units 141 , 142, and 143 which are repeated over the layer.
  • Each of the pixel or subpixel units represents a different color.
  • the subpixel units are for red, green, and blue. Although three subpixel units are shown in the figure, two or more than three may be used.
  • the different layers have the following range of thicknesses: anode 1 10, 500-5000 A, in some embodiments, 1000- 2000 A; hole injection layer 120, 50-2000 A, in some embodiments, 200- 1000 A; hole transport layer 130, 50-2000 A, in some embodiments, 200- 1000 A; photoactive layer 140, 10-2000 A, in some embodiments, 100- 1000 A; electron transport layer 150, 50-2000 A, in some embodiments, 100-1000 A; cathode 160, 200-10000 A, in some embodiments, 300-5000 A.
  • the desired ratio of layer thicknesses will depend on the exact nature of the materials used.
  • the diastereomeric pair of enantiomers having Formula I is useful as the emissive material in photoactive layer 140, having blue emission color.
  • the diastereomeric pair of enantiomers can be used alone or as a dopant in a host material.
  • the photoactive layer includes a host material and a composition having Formula I as a dopant. In some embodiments a second host material may be present. In some
  • the photoactive layer consists essentially of a host material and a composition having Formula I as a dopant, where features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiment are not present.
  • the photoactive layer consists essentially of a first host material, a second host material, and a composition having Formula I as a dopant, where features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiment are not present.
  • a second host material may be present.
  • the photoactive layer consists essentially of a host material and n diastereomeric pairs of enantiomers having Formula I as a dopant, where features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiment are not present.
  • the photoactive layer consists essentially of a first host material, a second host material, and n diastereomeric pairs of enantiomers having Formula I as a dopant, where features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiment are not present.
  • the photoactive layer consists essentially of a host material and three diastereomeric pairs of enantiomers having Formula I as a dopant, where features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiment are not present.
  • the photoactive layer consists essentially of a first host material, a second host material, and three diastereomeric pairs of enantiomers having Formula I as a dopant, where features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiment are not present.
  • the photoactive layer consists essentially of a host material and two diastereomeric pairs of enantiomers having
  • the photoactive layer consists essentially of a first host material, a second host material, and two diastereomeric pairs of enantiomers having Formula I as a dopant, where features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiment are not present.
  • the photoactive layer consists essentially of a host material and one diastereomeric pairs of enantiomers having
  • the photoactive layer consists essentially of a first host material, a second host material, and one diastereomeric pairs of enantiomers having Formula I as a dopant, where features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiment are not present.
  • the weight ratio of dopant to total host material is in the range of 5:95 to 70:30; in some embodiments, 10:90 to 20:80.
  • the host has a triplet energy level higher than that of the dopant, so that it does not quench the emission. In some embodiments, the host is selected from the group consisting of
  • carbazoles indolocarbazoles, triazines, aryl ketones, phenylpyridines, pyrimidines, phenanthrolines, triarylamines, deuterated analogs thereof, combinations thereof, and mixtures thereof.
  • the photoactive layer is intended to emit white light.
  • the photoactive layer comprises a host, a composition having Formula I, and one or more additional dopants emitting different colors, so that the overall emission is white.
  • the photoactive layer consists essentially of a host, a first dopant which is a composition having Formula I, and a second dopant, where the second dopant emits a different color than the first dopant, and where features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiment are not present.
  • the emission color of the second dopant is yellow.
  • the photoactive layer consists
  • the emission color of the second dopant is red and the emission color of the third dopant is green.
  • the photoactive layer is intended to emit white light.
  • the photoactive layer comprises a host, n diastereomeric pair of enantiomers of Formula I, and one or more additional dopants emitting different colors, so that the overall emission is white.
  • the photoactive layer consists essentially of a host, a first dopant which is n diastereomeric pairs of enantiomers having Formula I, and a second dopant, where the second dopant emits a different color than the first dopant, and where features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiment are not present.
  • the emission color of the second dopant is yellow.
  • the photoactive layer consists essentially of a host, a first dopant which is n diastereomeric pair of enantiomers having Formula I, a second dopant, and a third dopant, where features or elements that would materially alter the principle of operation or the distinguishing
  • the emission color of the second dopant is red and the emission color of the third dopant is green.
  • EL materials include, but are not limited to, small molecule organic fluorescent compounds, luminescent metal complexes, conjugated polymers, and mixtures thereof.
  • fluorescent compounds include, but are not limited to, chrysenes, pyrenes, perylenes, rubrenes, coumarins, anthracenes, thiadiazoles, derivatives thereof, arylamino derivatives thereof, and mixtures thereof.
  • metal complexes include, but are not limited to, metal chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum (Alq3);
  • cyclometalated iridium and platinum electroluminescent compounds such as complexes of iridium with phenylpyridine, phenylquinoline, or
  • conjugated polymers include, but are not limited to poly(phenylenevinylenes), polyfluorenes, poly(spirobifluorenes), polythiophenes, poly(p-phenylenes), copolymers thereof, and mixtures thereof.
  • red, orange and yellow light-emitting materials include, but are not limited to, complexes of Ir having phenylquinoline or
  • Red light-emitting materials have been disclosed in, for example, US patent 6,875,524, and published US application 2005-0158577.
  • the second and third dopants are N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl
  • the other layers in the device can be made of any materials which are known to be useful in such layers.
  • the anode 1 10 is an electrode that is particularly efficient for injecting positive charge carriers. It can be made of, for example materials containing a metal, mixed metal, alloy, metal oxide or mixed-metal oxide, or it can be a conducting polymer, and mixtures thereof. Suitable metals include the Group 1 1 metals, the metals in Groups 4, 5, and 6, and the Group 8-10 transition metals. If the anode is to be light-transmitting, mixed-metal oxides of Groups 12, 13 and 14 metals, such as indium-tin- oxide, are generally used.
  • the anode may also comprise an organic material such as polyaniline as described in "Flexible light-emitting diodes made from soluble conducting polymer," Nature vol. 357, pp 477 479 (1 1 June 1992). At least one of the anode and cathode should be at least partially transparent to allow the generated light to be observed.
  • the hole injection layer 120 comprises hole injection material and may have one or more functions in an organic electronic device, including but not limited to, planarization of the underlying layer, charge transport and/or charge injection properties, scavenging of impurities such as oxygen or metal ions, and other aspects to facilitate or to improve the performance of the organic electronic device.
  • the hole injection layer can be formed with polymeric materials, such as polyaniline (PANI) or polyethylenedioxythiophene (PEDOT), which are often doped with protonic acids.
  • the protonic acids can be, for example, poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1 -propanesulfonic acid), and the like.
  • the hole injection layer can comprise charge transfer compounds, and the like, such as copper phthalocyanine and the tetrathiafulvalene- tetracyanoquinodimethane system (TTF-TCNQ).
  • the hole injection layer comprises at least one electrically conductive polymer and at least one fluorinated acid polymer.
  • the hole injection layer is made from an aqueous dispersion of an electrically conducting polymer doped with a colloid-forming polymeric acid.
  • an electrically conducting polymer doped with a colloid-forming polymeric acid Such materials have been described in, for example, published U.S. patent applications US 2004/0102577, US
  • hole transport materials for layer 130 have been summarized for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Both hole transporting molecules and polymers can be used. Commonly used hole transporting molecules are: N,N'-diphenyl-N,N'-bis(3-methylphenyl)- [1 ,1 '-biphenyl]-4,4'-diamine (TPD), 1 ,1 -bis[(di-4-tolylamino)
  • TAPC phenyljcyclohexane
  • EPD phenyljcyclohexane
  • PDA tetrakis-(3- methylphenyl)-N,N,N',N'-2,5-phenylenediamine
  • TPS p-(diethylamino)benzaldehyde
  • DEH diphenylhydrazone
  • TPA triphenylamine
  • MPMP bis[4-(N,N- diethylamino)-2-methylphenyl](4-methylphenyl)methane
  • the hole transport layer comprises a hole transport polymer.
  • the hole transport polymer is a distyrylaryl compound.
  • the aryl group has two or more fused aromatic rings.
  • the aryl group is an acene.
  • acene refers to a hydrocarbon parent component that contains two or more ortho-lused benzene rings in a straight linear arrangement.
  • Other commonly used hole transporting polymers are polyvinylcarbazole, (phenylmethyl)-polysilane, and polyaniline. It is also possible to obtain hole transporting polymers by doping hole transporting molecules such as those mentioned above into polymers such as polystyrene and polycarbonate.
  • triarylamine polymers are used, especially triarylamine-fluorene copolymers.
  • the polymers and copolymers are crosslinkable. .
  • the hole transport layer further comprises a p-dopant.
  • the hole transport layer is doped with a p-dopant.
  • p-dopants include, but are not limited to, tetrafluorotetracyanoquinodimethane (F4-TCNQ) and perylene-3,4,9,10- tetracarboxylic-3,4,9,10-dianhydride (PTC DA).
  • electron transport materials which can be used for layer 150 include, but are not limited to, metal chelated oxinoid
  • metal quinolate derivatives such as tris(8- hydroxyquinolato)aluminum (AIQ), bis(2-methyl-8-quinolinolato)(p- phenylphenolato) aluminum (BAIq), tetrakis-(8-hydroxyquinolato)hafnium (HfQ) and tetrakis-(8-hydroxyquinolato)zirconium (ZrQ); and azole compounds such as 2- (4-biphenylyl)-5-(4-t-butylphenyl)-1 ,3,4-oxadiazole (PBD), 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1 ,2,4-triazole (TAZ), and 1 ,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivatives such as 2,3-bis(4-fluorophenyl)quinoxaline; phenan
  • the electron transport layer further comprises an n-dopant.
  • N-dopant materials are well known.
  • An anti-quenching layer may be present between the photoactive layer and the electron transport layer to prevent quenching of blue luminance by the electron transport layer.
  • the triplet energy of the anti-quenching material has to be higher than the triplet energy of the blue emitter.
  • the LUMO level of the anti-quenching material has to be shallow enough (with respect to the vacuum level) such that electron transfer between the emitter exciton and the anti-quenching material is endothermic.
  • the HOMO level of the anti-quenching material has to be deep enough (with respect to the vacuum level) such that electron transfer between the emitter exciton and the anti-quenching material is endothermic.
  • anti-quenching material is a large band-gap material with high triplet energy.
  • Examples of materials for the anti-quenching layer include, but are not limited to, tnphenylene, tnphenylene derivatives, carbazole, carbazole derivatives, and deuterated analogs thereof. Some specific materials include those shown below.
  • An optional electron injection layer may be deposited over the electron transport layer.
  • electron injection materials include, but are not limited to, Li-containing organometallic compounds, LiF, Li 2 O, Li quinolate, Cs-containing organometallic compounds, CsF, Cs 2 O, and CS2CO3. This layer may react with the underlying electron transport layer, the overlying cathode, or both.
  • the amount of material deposited is generally in the range of 1 - 100 A, in some embodiments 1 -10 A.
  • the cathode 160 is an electrode that is particularly efficient for injecting electrons or negative charge carriers.
  • the cathode can be any metal or nonmetal having a lower work function than the anode.
  • Materials for the cathode can be selected from alkali metals of Group 1 (e.g., Li, Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, including the rare earth elements and lanthanides, and the actinides. Materials such as aluminum, indium, calcium, barium, samarium and magnesium, as well as combinations, can be used. It is known to have other layers in organic electronic devices.
  • anode 1 10 and hole injection layer 120 there can be a layer (not shown) between the anode 1 10 and hole injection layer 120 to control the amount of positive charge injected and/or to provide band-gap matching of the layers, or to function as a protective layer.
  • Layers that are known in the art can be used, such as copper phthalocyanine, silicon oxy-nitride, fluorocarbons, silanes, or an ultra-thin layer of a metal, such as Pt.
  • some or all of anode layer 1 10, active layers 120, 130, 140, and 150, or cathode layer 160 can be surface-treated to increase charge carrier transport efficiency.
  • the choice of materials for each of the component layers is preferably determined by balancing the positive and negative charges in the emitter layer to provide a device with high electroluminescence efficiency.
  • each functional layer can be made up of more than one layer.
  • the device layers can be formed by any deposition technique, or combinations of techniques, including vapor deposition, liquid deposition, and thermal transfer.
  • the device is fabricated by liquid deposition of the hole injection layer, the hole transport layer, and the photoactive layer, and by vapor deposition of the anode, the electron transport layer, an electron injection layer and the cathode.
  • the hole injection layer can be deposited from any liquid medium in which it is dissolved or dispersed and from which it will form a film.
  • the liquid medium consists essentially of one or more organic solvents.
  • the liquid medium consists essentially of water or water and an organic solvent.
  • the hole injection material can be present in the liquid medium in an amount from 0.5 to 10 percent by weight.
  • the hole injection layer can be applied by any continuous or discontinuous liquid deposition technique. In one
  • the hole injection layer is applied by spin coating. In one embodiment, the hole injection layer is applied by ink jet printing. In one embodiment, the hole injection layer is applied by continuous nozzle printing. In one embodiment, the hole injection layer is applied by slot-die coating. After liquid deposition, the liquid medium can be removed in air, in an inert atmosphere, or by vacuum, at room temperature or with heating.
  • the hole transport layer can be deposited from any liquid medium in which it is dissolved or dispersed and from which it will form a film.
  • the liquid medium consists essentially of one or more organic solvents.
  • the liquid medium consists essentially of water or water and an organic solvent.
  • the organic solvent is an aromatic solvent.
  • the organic liquid is selected from chloroform, dichloromethane,
  • the hole transport material can be present in the liquid medium in a concentration of 0.2 to 2 percent by weight.
  • the hole transport layer can be applied by any continuous or discontinuous liquid deposition technique. In one embodiment, the hole transport layer is applied by spin coating. In one embodiment, the hole transport layer is applied by ink jet printing. In one embodiment, the hole transport layer is applied by continuous nozzle printing. In one embodiment, the hole transport layer is applied by slot-die coating. After liquid deposition, the liquid medium can be removed in air, in an inert atmosphere, or by vacuum, at room temperature or with heating.
  • the photoactive layer can be deposited from any liquid medium in which it is dissolved or dispersed and from which it will form a film.
  • the liquid medium consists essentially of one or more organic solvents.
  • the liquid medium consists essentially of water or water and an organic solvent.
  • the organic solvent is an aromatic solvent.
  • the organic solvent is selected from chloroform, dichloromethane, toluene, anisole, 2-butanone, 3-pentanone, butyl acetate, acetone, xylene, mesitylene, chlorobenzene, tetrahydrofuran, diethyl ether, trifluorotoluene, and mixtures thereof.
  • the photoactive material can be present in the liquid medium in a concentration of 0.2 to 2 percent by weight. Other weight percentages of photoactive material may be used depending upon the liquid medium.
  • the photoactive layer can be applied by any continuous or discontinuous liquid deposition technique. In one embodiment, the photoactive layer is applied by spin coating. In one embodiment, the photoactive layer is applied by ink jet printing. In one embodiment, the photoactive layer is applied by continuous nozzle printing. In one embodiment, the photoactive layer is applied by slot-die coating. After liquid deposition, the liquid medium can be removed in air, in an inert atmosphere, or by vacuum, at room temperature or with heating.
  • the electron transport layer can be deposited by any vapor deposition method. In one embodiment, it is deposited by thermal evaporation under vacuum.
  • the electron injection layer can be deposited by any vapor deposition method. In one embodiment, it is deposited by thermal evaporation under vacuum.
  • the cathode can be deposited by any vapor deposition method. In one embodiment, it is deposited by thermal evaporation under vacuum.
  • This example illustrates the preparation of Composition B1 .
  • a catalyst solution was prepared by combining Pd2(dba)3 (0.92 g, 0.90 mmol) and S-Phos (1 .6 g, 3.9 mmol) in toluene (30 ml_) and stirring the mixture at room temperature for 30 min.
  • 2,4-Dibromo-6-isopropylaniline (15.0 g, 51 .2 mmol)
  • phenylboronic acid (19.4 g, 143 mmol)
  • potassium phosphate monohydrate 70.7 g, 307 mmol
  • the reaction mixture was cooled to room temperature, diluted with 600 mL of ethyl acetate, filtered through a pad of Celite, ® washed several times with ethyl acetate, and concentrated under vacuum to afford an oil. Due to the large amount of material, the crude product was divided in half and chromatographed in two batches on pre-packed 340 g Biotage ® silica gel columns with ethyl acetate/hexane as the eluent.
  • the product containing fractions were concentrated to dryness to afford 2,4-diphenyl-6-isopropylaniline as a red oil.
  • the second batch contained a small amount of an impurity not observed in the first batch (5.4 g); it was further purified by redissolving in ethyl acetate and adding aqueous HCI dropwise to precipitate an off-white solid. The solid was filtered off and dissolved in a mixture of ethyl aceate and saturated
  • Step 4 4-(5'-isopropyl-[1 ,1 ':3',1 "-terphenyl]-4'-yl)-3-phenyl-5-(o-tolyl)-4H- 1 ,2,4-triazole
  • a catalyst solution was prepared by combining Pd 2 (dba) 3 (0.43 g, 0.47 mmol) and S-Phos (0.78 g, 1 .9 mmol) in toluene (60 ml_) and stirring the mixture at room temperature.
  • Step 5 Fac-tris (2-(4-(5'-isopropyl-[1 ,1 ':3',1 "-terphenyl]-4'-yl)-5-(o-tolyl)- 4H-1 ,2,4-triazol-3-yl)phenyl)iridium(lll) [mixture of all diastereomers], Composition B1
  • the solid ligand from above (1 .92 g, 3.80 mmol) and iridium tris- acetylacetonate (0.56 g, 1 .15 mmol) were premixed in a 5 dram vial under nitrogen in a glove box.
  • the mixture was placed in the 10 ml_ capacity stainless steel laboratory pressure reactor.
  • the mixture was equilibrated in a nitrogen atmosphere, sealed, and heated to an internal temperature of 256 °C. Heating was discontinued after 60 h at 256 - 257 °C.
  • the reactor was allowed to cool to room temperature and then vented. It was disassembled and the reactor tube washed with -200 ml_ of EtOAc followed by -200 ml_ of CH 2 CI 2 .
  • the washings were concentrated under vacuum to afford a solid.
  • Step 1 5-(tert-butyl)-[1 ,1 '-biphenyl]-2-amine
  • a catalyst solution was prepared by combining Pd 2 (dba) 3 (0.92 g, 1 .0 mmol) and S-Phos (1 .6 g, 3.9 mmol) in 30 ml_ of toluene under nitrogen and stirring the mixture at room temperature for 30 min.
  • 2- Bromo-4-tert-butylaniline (23.4 g, 102.4 mmol), phenylboronic acid (19.4 g, 143 mmol) and potassium phosphate monohydrate (70.7 g, 307 mmol) were combined in 300 mL of toluene and stirred rapidly under nitrogen 40 min.
  • the prepared catalyst mixture in 30 mL of toluene was added and the reaction mixture was stirred under nitrogen and heated to reflux.
  • the mixture was heated at reflux for a total of 2 h and then it was cooled to room temperature under nitrogen.
  • the mixture was diluted with 600 mL of ethyl acetate and filtered through a pad of Celite. ® The mixture was concentrated to dryness and a portion of it (17.0 g, 56%) was
  • Step 2 2-([1 ,1 '-biphenyl]-2-yl)-5-phenyl-1 ,3,4-oxadiazole
  • 2-biphenylcarboxylic acid (15.0 g, 75.7 mmol) was dissolved in 700 mL of anhydrous THF under nitrogen. The solution was treated with diisopropylethylamine (29.4 g, 227 mmol, 3.0 equiv) followed by 2-(7-Aza ⁇ 1 H-benzotriazoie-1 -y! 1 .1 ,3,3-tetramethyiuronium hexafiuorophosphate (31 .7 g, 83.2 mmol) and benzoyl hydrazine (10.3 g, 75.7 mmol).
  • the dichloromethane extracts were combined, washed once with 500 mL of water, dried over Na 2 SO , filtered, and concentrated to dryness. The resulting material was redissolved in dichloromethane and washed 5 times with 500 mL portions of water. The dichloromethane layer was dried over MgSO 4 , filtered, and concentrated to afford a solid. The solid was dissolved /suspended in dichloromethane and half (by weight) was chromatographed on a Biotage® 340 g silica gel column using a gradient of 5% to 40% ethyl acetate in hexane.
  • Step 4 Fac-tris-(2-(5-([1 ,1 '-biphenyl]-2-yl)-4-(5-(tert-butyl)-[1 ,1 '-biph 2-yl)-4H-1 ,2,4-triazol-3-yl)phenyl)iridium(lll), Composition B2.
  • the solid ligand from above (2.88 g, 5.70 mmol) and iridium tris- acetylacetonate (0.85 g, 1 .73 mmol) were premixed in a 5 dram vial under nitrogen in the glove box.
  • the mixture was placed in a 6.5 ml_ capacity stainless steel pressure reactor.
  • the mixture was equilibrated in a nitrogen atmosphere, sealed, and heated to an internal temperature of 253 °C.
  • the mixture was heated for 60 h and then allowed to slowly cool to room temperature while sealed.
  • the reactor was opened and the contents rinsed out with approximately 200 ml_ of dichloromethane.
  • the rinsings were concentrated and dried to afford a solid.
  • This example illustrates the isolation of a diastereomeric pair of enantiomers of Composition B2.
  • This example illustrates the preparation of Composition B3.
  • Step 1 4-(3-isopropyl-[1 ,1 '-biphenyl]-2-yl)-3-phenyl-4H-1 ,2,4-triazole
  • 2-phenyl-1 ,3,4-oxadiazole (3.25 g, 22.2 mmol) was placed in a 100 ml_ three neck flask and treated with a solution of 3-isopropyl-biphenyl-2- ylamine (4.70 g, 22.2 mmol) in 1 ,2- dichlorobenzene (4.5 ml_).
  • the resulting solution was stirred at room temperature under nitrogen and treated with one equivalent of trifluoroacetic acid (1 .65 ml_).
  • the mixture was stirred and heated at reflux overnight.
  • the mixture was then cooled to room temperature and treated with excess aqueous K2CO3 forming a gummy solid precipitate. This was extracted three times with ethyl acetate.
  • Step 2 3-bromo-4-(3-isopropyl-[1 ,1 '-biphenyl]-2-yl)-5-phenyl-4H-1 ,2,4- triazole
  • a catalyst solution was prepared by combining Pd2(dba)3 (0.24 g, 0.26 mmol) and S-Phos (0.43 g, 1 .04 mmol) in 33 mL of toluene under nitrogen and stirring the mixture at room temperature for 30 min.
  • the bromo-triazole from above (2.20 g, 5.26 mmol), 2-ethylphenylboronic acid (1 .58 g, 10.5 mmol) and potassium phosphate monohydrate (3.64 g, 15.8 mmol) were combined in 80 mL of toluene. The mixture was stirred rapidly under nitrogen and sparged with a stream of nitrogen bubbled through the mixture for 40 min.
  • the catalyst mixture was added and the reaction mixture was stirred under nitrogen and heated to reflux. The mixture was refluxed under nitrogen overnight. After 18 h, the mixture was cooled to room temperature under nitrogen.
  • the reaction mixture was diluted with an equal volume (1 15 mL) of ethyl acetate and filtered through a Celite® pad. The pad was washed several times with ethyl acetate into the filtrate. The filtrate was concentrated to afford a glassy solid.
  • the solid was chromatographed on a Biotage® 340 g silica gel column. The column was eluted with a gradient of 4% to 40% ethyl acetate in hexane. The main fractions were combined and concentrated to afford 1 .33 g (57% yield) of a pale yellow foam which crystallized to a pale yellow solid.
  • the ligand from above (1 .33 g, 3.00 mmol) and iridium tris- acetylacetonate (0.46 g, 0.94 mmol) were premixed in a 50 mL flask under nitrogen in the glove box. The mixture was placed in a 6.5 mL capacity stainless steel pressure reactor. The vessel was sealed tightly under nitrogen. The pressure vessel was then heated over at an internal melt temperature of 248 °C for 60 h. After cooling, the crude product was chromatographed on a Biotage® 340 g silica gel column which was eluted with a gradient of 2% to 20% ethyl acetate in hexane.
  • UPLC-MS indicated a purity of 99.3% (however, this includes a small shoulder peak corresponding to a trace amount of another iridium complex in which an ethyl group has been lost from one of the three ligands).
  • Parent ion + 1 peak observed at m/z 1521 .00.
  • the 1 H NMR indicates that this material is one of the two possible MMP/PPM diastereomers, with the relative configuration at Ir undetermined; that is, it is either B3-c, ⁇ - ⁇ / ⁇ - ⁇ , or B3-b, ⁇ - ⁇ / ⁇ - PMM, shown below.
  • Stereochemistry at Ir center is ⁇
  • Stereochemistry at Ir center is ⁇
  • This example illustrates the preparation of Composition B4 and the isolation of diastereomeric pairs of enantiomers of Composition B4.
  • Step 1 4-(3-isopropyl-[1 ,1 '-biphenyl]-2-yl)-3-phenyl-5-(o-tolyl)-4H-1 ,2,4- triazole
  • a reaction mixture containing 3-bromo-4-(3-isopropyl-[1 ,1 '- biphenyl]-2-yl)-5-phenyl-4H-1 ,2,4-triazole (see Synthesis Example 9, Step 2, 4.40 g, 10.5 mmol), o-tolylboronic acid (2.85 g, 21 .03mmol), Pd 2 dba 3 (0.288 g, 0.03 equiv), S-Phos (0.517 g, 0.12 eq.), K 3 PO 4 (7.26 g, 3 equiv) in 150 ml_ of toluene was heated at reflux for 2 h under nitrogen.
  • the reaction mixture was cooled to room temperature, and then passed through a silica gel bed.
  • the filtrate was concentrated under reduced pressure, then purified by silica gel column chromatography (10- 30% ethyl acetate in hexane) to provide 3.7g (82%) of the triazole ligand as a white solid.
  • Step 2 fr/ ' s-3-(2-methylphenyl)-5-phenyl-4-[3-(propan-2-yl) biphenyl-2-yl]- -1 ,2,4-triazole-iridium, Composition B4
  • the first compound (60mg, 4.4% yield) was determined to be B4-a, ⁇ / ⁇ , by X-ray crystallography.
  • Stereochemistry at Ir center is ⁇
  • Stereochemistry at Ir center is ⁇
  • the second compound (200mg, 14.8% yield) was determined to be B4-b, ⁇ / ⁇ , by X-ray crystallography.
  • HIJ-1 is an electrically conductive polymer doped with a polymeric
  • HT-1 is a triarylamine-containing polymer.
  • Such materials have been described in, for example, published PCT application
  • ET-1 is a metal quinolate complex.
  • hole injection layer HIJ-1 (50 nm)
  • hole transport layer HT-1 (20 nm)
  • anti-quenching layer Same as host in photoactive layer (10nm)
  • electron transport layer ET-1 (10 nm)
  • OLED devices were fabricated by a combination of solution processing and thermal evaporation techniques.
  • Patterned indium tin oxide (ITO) coated glass substrates from Thin Film Devices, Inc were used. These ITO substrates are based on Corning 1737 glass coated with ITO having a sheet resistance of 30 ohms/square and 80% light transmission.
  • the patterned ITO substrates were cleaned ultrasonically in aqueous detergent solution and rinsed with distilled water.
  • the patterned ITO was subsequently cleaned ultrasonically in acetone, rinsed with isopropanol, and dried in a stream of nitrogen.
  • ITO substrates were treated with UV ozone for 10 minutes.
  • an aqueous dispersion of HIJ-1 was spin-coated over the ITO surface and heated to remove solvent.
  • the substrates were then spin-coated with a hole transport solution, and then heated to remove solvent.
  • the substrates were masked and placed in a vacuum chamber.
  • the photoactive layer, the electron transport layer and the anti-quenching layer were deposited by thermal evaporation, followed by a layer of CsF.
  • Masks were then changed in vacuo and a layer of Al was deposited by thermal evaporation.
  • the chamber was vented, and the devices were encapsulated using a glass lid, dessicant, and UV curable epoxy.
  • E.Q.E. is the external quantum efficiency
  • EL peak is the wavelength of maximum emission
  • CIE(x,y) are the x and y color coordinates according to the CLE. chromaticity scale (Commission Internationale de L'Eclairage, 1931 ); T70 is a measure of lifetime and is the time to reach 70% of initial luminance.
  • This example illustrates the use of a diastereomeric pair of enantiomers from Composition B2 as the light emitting material in a device.
  • E.Q.E. is the external quantum efficiency
  • EL peak is the wavelength of maximum emission
  • CIE(x,y) are the x and y color coordinates according to the CLE. chromaticity scale (Commission Internationale de L'Eclairage, 1931 ); T70 is a measure of lifetime and is the time to reach 70% of initial luminance.
  • the dopant is a 50/50 mixture of PPP/MMM enantiomers, with the stereochemistry at Ir ( ⁇ or ⁇ ) undetermined.
  • E.Q.E. is the external quantum efficiency
  • EL peak is the wavelength of maximum emission
  • CIE(x,y) are the x and y color coordinates according to the CLE. chromaticity scale (Commission Internationale de L'Eclairage, 1931 ); T70 is a measure of lifetime and is the time to reach 70% of initial luminance.
  • the dopant is a 50/50 mixture of PMM/MPP enantiomers, with the the stereochemistry at Ir ( ⁇ or ⁇ ) undetermined.
  • CIE(x,y) are the x and y color coordinates according to the CLE.
  • chromaticity scale (Commission Internationale de L'Eclairage, 1931 );
  • T70 is a measure of lifetime and is the time to reach 70% of initial luminance.

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Abstract

L'invention concerne une composition qui peut être être séparée en paires diastéréoisomères d'énantiomères. Le composé répond à la formule (Formule I). Dans la formule I : Ar' peut représenter un groupe aryle ou aryle deutéré; R1 peut représenter H, D, un groupe alkyle, un groupe silyle, un groupe aryle ou un analogue deutéré de ces derniers; R2 est différent de R1 et peut représenter H, D, un groupe alkyle, un groupe silyle, un groupe aryle ou un analogue deutéré de ces derniers, à condition que seulement l'un de R1 et R2 représente H ou D; R3 est identique ou différent à chaque occurrence et peut représenter D, un groupe alkyle, un groupe silyle, un groupe aryle ou un analogue deutéré de ces derniers; a est un nombre entier de 0 à 3; et b est un nombre entier de 0 à 4.
PCT/US2015/025720 2014-05-16 2015-04-14 Composé luminescent bleu et ses diastéréoisomères WO2015175130A1 (fr)

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