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US20170324049A1 - Organic Electroluminescent Materials and Devices - Google Patents

Organic Electroluminescent Materials and Devices Download PDF

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US20170324049A1
US20170324049A1 US15/475,463 US201715475463A US2017324049A1 US 20170324049 A1 US20170324049 A1 US 20170324049A1 US 201715475463 A US201715475463 A US 201715475463A US 2017324049 A1 US2017324049 A1 US 2017324049A1
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organic
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alkyl
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Jui-Yi Tsai
Chuanjun Xia
Walter Yeager
Alexey Borisovich Dyatkin
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Universal Display Corp
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Universal Display Corp
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Assigned to UNIVERSAL DISPLAY CORPORATION reassignment UNIVERSAL DISPLAY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DYATKIN, ALEXEY BORISOVICH, TSAI, JUI-YI, YEAGER, WALTER, XIA, CHUANJUN
Priority to KR1020170056373A priority patent/KR102514223B1/en
Publication of US20170324049A1 publication Critical patent/US20170324049A1/en
Priority to US17/236,282 priority patent/US12048237B2/en
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    • H01L51/0085—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • 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
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    • 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
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H01L51/0054—
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    • 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
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    • 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
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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    • 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
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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    • 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
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • 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
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to compounds for use as emitters, and devices, such as organic light emitting diodes, including the same.
  • 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 diodes/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.
  • 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.
  • the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs.
  • the white OLED can be either a single EML device or a stack structure. 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.
  • a compound that has the structure of (L A ) n Ir(L B ) 3-n represented by Formula I shown below:
  • R 2 , R 3 , R 4 and R 5 each represent monosubstitution, disubstitution, trisubstitution, tetrasubstitution, or no substitution;
  • R 1 is an aryl or heteroaryl comprising at least one group selected from group A consisting of:
  • R 1 can be further substituted with one or more substituents selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, and combinations thereof;
  • R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, and combinations thereof;
  • n 1 or 2.
  • an organic light emitting diode/device is also provided.
  • the OLED can include an anode, a cathode, and an organic layer, disposed between the anode and the cathode.
  • the organic layer can include a compound of Formula I.
  • the organic light emitting device is incorporated into a device selected from a consumer product, an electronic component module, and/or a lighting panel.
  • a consumer product comprising one or more organic light emitting devices.
  • the organic light emitting device can include an anode, a cathode, and an organic layer, disposed between the anode and the cathode, wherein the organic layer can include a compound of Formula I.
  • the consumer product can be a flat panel display, a computer monitor, a medical monitors television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, and/or a sign.
  • PDA personal digital assistant
  • a formulation containing a compound of Formula I is provided.
  • 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.
  • 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 can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays.
  • Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), wearable device, laptop computers, digital cameras, camcorders, viewfinders, micro-displays that are less than 2 inches diagonal, 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, or a sign.
  • PDAs personal digital assistants
  • wearable device laptop computers, digital cameras, camcorders, viewfinders, micro-displays that are less than 2 inches diagonal, 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, 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
  • 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 includes fluorine, chlorine, bromine, and iodine.
  • alkyl as used herein contemplates both straight and branched chain alkyl radicals.
  • Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted.
  • cycloalkyl as used herein contemplates cyclic alkyl radicals.
  • Preferred cycloalkyl groups are those containing 3 to 10 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.
  • alkenyl as used herein contemplates both straight and branched chain alkene radicals.
  • Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl group may be optionally substituted.
  • alkynyl as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.
  • aralkyl or “atylalkyl” as used herein are used interchangeably and contemplate an alkyl group that has as a substituent an aromatic group. Additionally, the aralkyl group may be optionally substituted.
  • heterocyclic group contemplates aromatic and non-aromatic cyclic radicals.
  • Hetero-aromatic cyclic radicals also means heteroaryl.
  • Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperdino, pyrrolidino, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like. Additionally, the heterocyclic group may be optionally substituted.
  • aryl or “aromatic group” as used herein contemplates single-ring groups and polycyclic ring systems.
  • the polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls.
  • Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons.
  • Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, cluysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted.
  • heteroatyl contemplates single-ring hetero-aromatic groups that may include from one to five heteroatoms.
  • heteroaryl also includes polycyclic hetero-aromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls.
  • Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms.
  • Suitable heteroaryl groups include 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, qui
  • alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl may be unsubstituted or may be substituted with one or more substituents selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
  • substituted indicates that a substituent other than H is bonded to the relevant position, such as carbon.
  • R 1 is mono-substituted
  • one R 1 must be other than H.
  • R 1 is di-substituted
  • two of R 1 must be other than H.
  • R 1 is hydrogen for all available positions.
  • aza-dibenzofuran i.e. aza-dibenzofuran, aza-dibenzothiophene, etc.
  • azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f, h]quinoline.
  • the conversion of electrical energy into light is mediated by excitons. It is the properties of the excitons that primarily determine the overall luminescent efficiency of the device.
  • the exciton formation process in OLEDs begins with electrons and holes injected at the electrodes. Dopants with deep LUMOs (more reducible LUMOs) generally lead to effective electron trapping and yield high efficiency OLED devices.
  • a series of heteroleptic tris-cyclometalated iridium (III) complexes that have deep LUMOs and are capable of producing high efficiency OLED devices.
  • the present invention includes a compound having the structure of (L A ) n Ir(L B ) 3-n represented by Formula I:
  • R 2 , R 3 , R 4 and R 5 each represent monosubstitution, disubstitution, trisubstitution, tetrasubstitution, or no substitution;
  • R 1 is an aryl or heteroaryl comprising at least one group selected from group A consisting of:
  • R 1 can be further substituted with one or more substituents selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, and combinations thereof;
  • R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, and combinations thereof;
  • n 1 or 2.
  • n 1
  • R 1 is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • R 1 ′ and R 2 ′ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;
  • R 1 ′ and R 2 ′ is not hydrogen or deuterium
  • A is a 5-membered or 6-membered carbocyclic or heterocyclic aromatic ring that is optionally further substituted;
  • R 1 ′, R 2 ′, and ring A comprise at least one group selected from group A.
  • the compound has the formula:
  • R 8 represents monosubstitution, disubstitution, trisubstitution, or no substitution
  • R 6 , R 7 , and R 8 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;
  • R 6 , R 7 , and R 8 comprises at least one group selected from group A.
  • the compound has the formula:
  • X 1 , X 2 , X 3 , X 4 , and X 5 are each independently selected from the group consisting of carbon, and nitrogen, and wherein at least one of X 1 , X 2 , X 3 , X 4 , and X 5 is nitrogen; and
  • R is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, and combinations thereof.
  • L A is selected from the group consisting of:
  • L B is selected from the group consisting of:
  • H H H 201 CH 3 H H 202. H CH 3 H 203. H H CH 3 204. CH 3 CH 3 H 205. CH 3 H CH 3 206. H CH 3 CH 3 207. CH 3 CH 3 CH 3 208. H H H 209. CH 3 H CH 3 210. H CH 3 H 211. H H CH 3 212. CH 3 CH 3 H 213. CH 3 H CH 3 214. H CH 3 CH 3 215. CH 3 CH 3 CH 3 216. H H H 217. CH 3 H CH 3 218. H CH 3 H 219. H H CH 3 220. CH 3 CH 3 H 221. CH 3 H CH 3 222. H CH 3 CH 3 223. CH 3 CH 3 CH 3 224. H H H H 225. CH 3 H H 226.
  • CH 3 CH 3 CH 3 280 H H H H 281. CH 3 H CH 3 282. H CH 3 H 283. H H CH 3 284. CH 3 CH 3 H 285. CH 3 H CH 3 286. H CH 3 CH 3 287. CH 3 CH 3 CH 3 288. H H H 289. CH 3 H CH 3 290. H CH 3 H 291. H H CH 3 292. CH 3 CH 3 H 293. CH 3 H CH 3 294. H CH 3 CH 3 295. CH 3 CH 3 CH 3 296. H H H 297. CH 3 H H 298. H CH 3 H 299. H H CH 3 300. CH 3 CH 3 H 301. CH 3 H CH 3 302. H CH 3 CH 3 303. CH 3 CH 3 CH 3 304. H H H H 305. CH 3 H CH 3 306.
  • CD 2 CH 2 CF 3 CD 3 CD 3 600 CD 3 CD 2 CH 2 CF 3 CD 3 CD 3 601. H H CD 2 CH 2 CF 3 H 602. CD 3 H CD 2 CH 2 CF 3 H 603. H CD 3 CD 2 CH 2 CF 3 H 604. H H CD 2 CH 2 CF 3 CD 3 605. CD 3 CD 3 CD 2 CH 2 CF 3 H 606. CD 3 H CD 2 CH 2 CF 3 CD 3 607. H CD 3 CD 2 CH 2 CF 3 CD 3 608. CD 3 CD 3 CD 2 CH 2 CF 3 CD 3 609. H H H 610. CD 3 H CD 3 611. H CD 3 H 612. H H CD 3 613. CD 3 CD 3 H 614. CD 3 H CD 3 615. H CD 3 CD 3 616.
  • CD(CH 3 ) 2 H CD 2 C(CH 3 ) 2 CF 3 H 760.
  • C(CH 3 ) 3 H CD(CH 3 ) 2 H 768.
  • C(CH 3 ) 3 H CD 2 CH(CH 3 ) 2 H 769.
  • CD 2 C(CH 3 ) 3 H CD 2 C(CH 3 ) 3 H 784.
  • CD 2 C(CH 3 ) 3 H CD 2 CH 2 CF 3 H 785.
  • CD 2 C(CH 3 ) 3 H CD 2 C(CH 3 ) 2 CF 3 H 786.
  • the compound is the Compound x having the Formula Ir(L Ai )(L Bj ) 2 ;
  • x 856i+j ⁇ 856; i is an integer from 1 to 111; and/is an integer from 1 to 856; and
  • L B1 to L B856 have the following structure:
  • L B1 to L B856 are defined according to the above table.
  • the compound can be an emissive dopant.
  • the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
  • TADF thermally activated delayed fluorescence
  • an OLED is also provided.
  • the OLED includes an anode, a cathode, and an organic layer disposed between the anode and the cathode.
  • the organic layer may include a host and a phosphorescent dopant.
  • the organic layer can include a compound according to Formula I, and its variations as described herein.
  • the OLED can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel.
  • the organic layer 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.
  • a consumer product comprising an OLED
  • the OLED may include an anode, a cathode, and an organic layer disposed between the anode and the cathode.
  • the organic layer may include a host and one or more emitter dopants.
  • the organic layer includes a compound of Formula I.
  • Non-limiting examples of consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), wearable device, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays that are less than 2 inches diagonal, 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, and/or signs.
  • PDAs personal digital assistants
  • 3-D displays that are less than 2 inches diagonal
  • 3-D displays virtual reality or augmented reality displays
  • vehicles video walls comprising multiple displays tiled together, theater or stadium screens, and/or signs.
  • the organic layer can also include a host.
  • a host In some embodiments, two or more hosts are preferred.
  • the hosts used maybe a) bipolar, b) electron transporting, c) hole transporting or d) wide band gap materials that play little role in charge transport.
  • the host can include a metal complex.
  • 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 , and C n H 2n —Ar 1 , or the host has 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 an inorganic compound.
  • a Zn containing inorganic material e.g. ZnS.
  • the host can be a compound comprising at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
  • the host can include a metal complex.
  • the host can be, but is not limited to, a specific compound selected from the group consisting of:
  • a formulation that comprises a compound according to Formula I is described.
  • 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 charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity.
  • the conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved.
  • Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
  • Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804 and US2012146012.
  • 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 are not limited 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 phosphoric 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 of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, cluysene, perylene, and azulene; the group consisting of 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
  • Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroatyl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
  • a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,
  • Ar 1 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 are not limited 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.
  • Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, US06517957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025,
  • An electron blocking layer may be used to reduce the number of electrons and/or excitons that leave the emissive layer.
  • the presence of such a blocking layer in a device may result in substantially higher efficiencies, and or longer lifetime, 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.
  • the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface.
  • the EBL material has a higher LUMO (closer to the vacuum level) and or higher triplet energy than one or more of the hosts closest to the EBL interface.
  • the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
  • 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. 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 101 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 of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, cluysene, perylene, and azulene; the group consisting of 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
  • Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of 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 deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, ary
  • the host compound contains at least one of the following groups in the molecule:
  • each of 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, heteroatyl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroatyl, it has the similar definition as Ar's mentioned above.
  • 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.
  • Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S.
  • One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure.
  • the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials.
  • suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
  • Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, US06699599, US06916554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US2006013446
  • 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 and/or longer lifetime 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.
  • the HBL material has a lower HOMO (further from the vacuum level) and or higher triplet energy than the emitter closest to the HBL interface.
  • the HBL material has a lower HOMO (further from the vacuum level) and or higher triplet energy than one or more of the hosts closest to the HBL interface.
  • 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 heteroalyl, it has the similar definition as Ar's mentioned above.
  • Ar 1 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.
  • Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S.
  • the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually.
  • Typical CGL materials include n and p conductivity dopants used in the transport layers.
  • the hydrogen atoms can be partially or fully deuterated.
  • any specifically listed substituent such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof.
  • classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
  • the reaction mixture was cooled to room temperature, diluted with 300 mL water and then was extracted with 2 ⁇ 350 mL of ethyl acetate. These extracts were combined and were washed with aqueous LiCl. The extracts were dried over magnesium sulfate and filtered and concentrated under vacuum. The crude residue was subjected to column chromatography on silica gel, eluting with a 15-20% ethyl acetate/toluene gradient mixture, providing 1-(3-methylpyrazin-2-yl)-2-phenyl-1H-benzo[d]imidazole (7.0 g, 24.45 mmol, 71.5% yield) as a tan solid.
  • the reaction mixture was diluted with 300 mL water and was extracted with 3 ⁇ 250 mL ethyl acetate. The extracts were combined and washed with aqueous LiCl followed by drying over magnesium sulfate. The extract was filtered and concentrated under vacuum. The crude residue was subjected to column chromatography on silica gel columns, eluted with a 15-20% ethyl acetate/toluene gradient mixture, providing 1-(3-(1methyl-d3)pyrazin-2-yl)-2-phenyl-1H-benzo[d]imidazole (2.95 g, 10.20 mmol, 40.9% yield) as a tan solid.
  • the iridium salt (4.6 g, 6.44 mmol) and 1-(3-(methyl-d3)pyrazin-2-yl)-2-phenyl-1H-benzo[d]imidazole (2.95 g, 10.20 mmol) were suspended in a 120 mL methanol and ethanol (1/1;v/v) mixture, degassed with nitrogen, and then immersed in an oil bath at 75° C. for 16 h. HPLC showed trace product. The reaction mixture was evaporated under reduced pressure and 60 mL of fresh ethanol was added. This mixture was degassed again and heated in an oil bath set at 90° C. for 24 hours. HPLC still showed very little product formation. The ethanol was removed and was replaced with DMF and 2-ethoxyethanol.
  • the reaction mixture was degassed with nitrogen and was heated in an oil bath at 130° C. for 2 1/2 days. The reaction mixture was then cooled down to room temperature. The solvents were removed under vacuum and the crude residue was subjected to column chromatography on a silica gel column, eluted with DCM followed by DCM/ethyl acetate (1/1;v/v). The solvents were removed and the product residue was purified by column chromatography.
  • the first product eluted from the column was isolated as an orange solid. This material was dissolved in 300 mL DCM and passed through a pad of activated basic alumina The filtrate was evaporated under reduced vacuum. This residue was passed through 7 ⁇ 120g silica gel columns The columns were eluted with 5-10% ethyl acetate/toluene. The pure product fractions were combined and concentrated under vacuum, yielding the iridium complex as an orange solid (0.60g, 0.76 mmol, 11.8% yield)
  • N1-(4-methylpyrimidin-5-yl)benzene-1,2-diamine (7.95 g, 39.7 mmol)
  • benzaldehyde (5.18 g, 48.8 mmol)
  • Na 2 S 2 O 5 15.09 g, 79 mmol
  • the reaction mixture was heated for 16 h at 125° C. open to air.
  • the reaction mixture was then cooled down, diluted with EtOAc, and washed with brine and LiCl aq.10% solution.
  • All example devices were fabricated by high vacuum ( ⁇ 10 ⁇ 7 Torr) thermal evaporation.
  • the anode electrode was 750 ⁇ of indium tin oxide (ITO).
  • the cathode consisted of 10 ⁇ of Liq (8-hydroxyquinoline lithium) followed by 1,000 ⁇ of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box ( ⁇ 1 ppm of H 2 O 2 O 2 ) immediately after fabrication with a moisture getter incorporated inside the package.
  • the organic stack of the device examples consisted of sequentially, from the ITO Surface: 100 ⁇ of HAT-CN as the hole injection layer (HIL); 450 ⁇ of HTM as a hole transporting layer (HTL); emissive layer (EML) with thickness 400 ⁇ .
  • HIL hole injection layer
  • HTL hole transporting layer
  • EML emissive layer
  • Device structure is shown in the table 1. Table 1 shows the schematic device structure. The chemical structures of the device materials are shown below.

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Abstract

The present invention includes a new series of heteroleptic iridium complexes that demonstrate high efficiency in OLED device.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application claims priority to U.S. Provisional Patent Application Ser. No. 62/332,239, filed May 5, 2016, the entire contents of which is incorporated herein by reference.
    • FIELD
  • The present invention relates to compounds for use as emitters, and devices, such as organic light emitting diodes, including the same.
    • 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 diodes/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. Alternatively the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single EML device or a stack structure. 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 US20170324049A1-20171109-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.
  • There is need in the art for novel emitters which can be used for electroluminescent devices. The present invention addresses this unmet need.
    • SUMMARY
  • According to an embodiment, a compound is provided that has the structure of (LA)nIr(LB)3-n represented by Formula I shown below:
  • Figure US20170324049A1-20171109-C00002
  • wherein R2, R3, R4 and R5 each represent monosubstitution, disubstitution, trisubstitution, tetrasubstitution, or no substitution;
  • wherein R1 is an aryl or heteroaryl comprising at least one group selected from group A consisting of:
  • Figure US20170324049A1-20171109-C00003
    Figure US20170324049A1-20171109-C00004
    Figure US20170324049A1-20171109-C00005
  • wherein R1 can be further substituted with one or more substituents selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, and combinations thereof;
  • wherein R2, R3, R4, and R5 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, and combinations thereof; and
  • wherein n is 1 or 2.
  • According to another embodiment, an organic light emitting diode/device (OLED) is also provided. The OLED can include an anode, a cathode, and an organic layer, disposed between the anode and the cathode. The organic layer can include a compound of Formula I. According to yet another embodiment, the organic light emitting device is incorporated into a device selected from a consumer product, an electronic component module, and/or a lighting panel.
  • According to another embodiment, a consumer product comprising one or more organic light emitting devices is also provided. The organic light emitting device can include an anode, a cathode, and an organic layer, disposed between the anode and the cathode, wherein the organic layer can include a compound of Formula I. The consumer product can be a flat panel display, a computer monitor, a medical monitors television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, and/or a sign.
  • According to another embodiment, a formulation containing a compound of Formula I is provided.
    • 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.
    •  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”), 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 can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), wearable device, laptop computers, digital cameras, camcorders, viewfinders, micro-displays that are less than 2 inches diagonal, 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, 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 term “halo,” “halogen,” or “halide” as used herein includes fluorine, chlorine, bromine, and iodine.
  • The term “alkyl” as used herein contemplates both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted.
  • The term “cycloalkyl” as used herein contemplates cyclic alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 10 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.
  • The term “alkenyl” as used herein contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl group may be optionally substituted.
  • The term “alkynyl” as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.
  • The terms “aralkyl” or “atylalkyl” as used herein are used interchangeably and contemplate an alkyl group that has as a substituent an aromatic group. Additionally, the aralkyl group may be optionally substituted.
  • The term “heterocyclic group” as used herein contemplates aromatic and non-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also means heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperdino, pyrrolidino, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like. Additionally, the heterocyclic group may be optionally substituted.
  • The term “aryl” or “aromatic group” as used herein contemplates single-ring groups and polycyclic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, cluysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted.
  • The term “heteroatyl” as used herein contemplates single-ring hetero-aromatic groups that may include from one to five heteroatoms. The term heteroaryl also includes polycyclic hetero-aromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include 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, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.
  • The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl may be unsubstituted or may be substituted with one or more substituents selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
  • As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant position, such as carbon. Thus, for example, where R1 is mono-substituted, then one R1 must be other than H. Similarly, where R1 is di-substituted, then two of R1 must be other than H. Similarly, where R1 is unsubstituted, R1 is hydrogen for all available positions.
  • The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, 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.
  • It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofutyl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
  • In an OLED device, the conversion of electrical energy into light is mediated by excitons. It is the properties of the excitons that primarily determine the overall luminescent efficiency of the device. The exciton formation process in OLEDs begins with electrons and holes injected at the electrodes. Dopants with deep LUMOs (more reducible LUMOs) generally lead to effective electron trapping and yield high efficiency OLED devices.
  • In one aspect of this invention, a series of heteroleptic tris-cyclometalated iridium (III) complexes that have deep LUMOs and are capable of producing high efficiency OLED devices.
    • Compounds of the Invention
  • In one aspect, the present invention includes a compound having the structure of (LA)nIr(LB)3-n represented by Formula I:
  • Figure US20170324049A1-20171109-C00006
  • wherein R2, R3, R4 and R5 each represent monosubstitution, disubstitution, trisubstitution, tetrasubstitution, or no substitution;
  • wherein R1 is an aryl or heteroaryl comprising at least one group selected from group A consisting of:
  • Figure US20170324049A1-20171109-C00007
    Figure US20170324049A1-20171109-C00008
    Figure US20170324049A1-20171109-C00009
  • wherein R1 can be further substituted with one or more substituents selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, and combinations thereof;
  • wherein R2, R3, R4, and R5 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, and combinations thereof; and
  • wherein n is 1 or 2.
  • In one embodiment, n is 1.
  • In one embodiment, R1 is
  • Figure US20170324049A1-20171109-C00010
  • wherein R1′ and R2′ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;
  • wherein at least one of R1′ and R2′ is not hydrogen or deuterium;
  • wherein A is a 5-membered or 6-membered carbocyclic or heterocyclic aromatic ring that is optionally further substituted; and
  • wherein at least one of R1′, R2′, and ring A comprise at least one group selected from group A.
  • In one embodiment, the compound has the formula:
  • Figure US20170324049A1-20171109-C00011
  • wherein R8 represents monosubstitution, disubstitution, trisubstitution, or no substitution;
  • wherein R6, R7, and R8 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; and
  • wherein at least one of R6, R7, and R8 comprises at least one group selected from group A.
  • In one embodiment, the compound has the formula:
  • Figure US20170324049A1-20171109-C00012
  • wherein X1, X2, X3, X4, and X5 are each independently selected from the group consisting of carbon, and nitrogen, and wherein at least one of X1, X2, X3, X4, and X5 is nitrogen; and
  • wherein R is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, and combinations thereof.
  • In one embodiment, LA is selected from the group consisting of:
  • Figure US20170324049A1-20171109-C00013
    Figure US20170324049A1-20171109-C00014
    Figure US20170324049A1-20171109-C00015
    Figure US20170324049A1-20171109-C00016
    Figure US20170324049A1-20171109-C00017
    Figure US20170324049A1-20171109-C00018
    Figure US20170324049A1-20171109-C00019
    Figure US20170324049A1-20171109-C00020
    Figure US20170324049A1-20171109-C00021
    Figure US20170324049A1-20171109-C00022
    Figure US20170324049A1-20171109-C00023
    Figure US20170324049A1-20171109-C00024
    Figure US20170324049A1-20171109-C00025
    Figure US20170324049A1-20171109-C00026
    Figure US20170324049A1-20171109-C00027
    Figure US20170324049A1-20171109-C00028
    Figure US20170324049A1-20171109-C00029
    Figure US20170324049A1-20171109-C00030
    Figure US20170324049A1-20171109-C00031
    Figure US20170324049A1-20171109-C00032
  • In one embodiment, LB is selected from the group consisting of:
  • LB
    Figure US20170324049A1-20171109-C00033
    LB RB1 RB2 RB3 RB4
    1. H H H H
    2. CH3 H H H
    3. H CH3 H H
    4. H H CH3 H
    5. H H H CH3
    6. CH3 H CH3 H
    7. CH3 H H CH3
    8. H CH3 CH3 H
    9. H CH3 H CH3
    10. H H CH3 CH3
    11. CH3 CH3 CH3 H
    12. CH3 CH3 H CH3
    13. CH3 H CH3 CH3
    14. H CH3 CH3 CH3
    15. CH3 CH3 CH3 CH3
    16. CH2CH3 H H H
    17. CH2CH3 CH3 H CH3
    18. CH2CH3 H CH3 H
    19. CH2CH3 H H CH3
    20. CH2CH3 CH3 CH3 H
    21. CH2CH3 CH3 H CH3
    22. CH2CH3 H CH3 CH3
    23. CH2CH3 CH3 CH3 CH3
    24. H CH2CH3 H H
    25. CH3 CH2CH3 H CH3
    26. H CH2CH3 CH3 H
    27. H CH2CH3 H CH3
    28. CH3 CH2CH3 CH3 H
    29. CH3 CH2CH3 H CH3
    30. H CH2CH3 CH3 CH3
    31. CH3 CH2CH3 CH3 CH3
    32. H H CH2CH3 H
    33. CH3 H CH2CH3 H
    34. H CH3 CH2CH3 H
    35. H H CH2CH3 CH3
    36. CH3 CH3 CH2CH3 H
    37. CH3 H CH2CH3 CH3
    38. H CH3 CH2CH3 CH3
    39. CH3 CH3 CH2CH3 CH3
    40. CH(CH3)2 H H H
    41. CH(CH3)2 CH3 H CH3
    42. CH(CH3)2 H CH3 H
    43. CH(CH3)2 H H CH3
    44. CH(CH3)2 CH3 CH3 H
    45. CH(CH3)2 CH3 H CH3
    46. CH(CH3)2 H CH3 CH3
    47. CH(CH3)2 CH3 CH3 CH3
    48. H CH(CH3)2 H H
    49. CH3 CH(CH3)2 H CH3
    50. H CH(CH3)2 CH3 H
    51. H CH(CH3)2 H CH3
    52. CH3 CH(CH3)2 CH3 H
    53. CH3 CH(CH3)2 H CH3
    54. H CH(CH3)2 CH3 CH3
    55. CH3 CH(CH3)2 CH3 CH3
    56. H H CH(CH3)2 H
    57. CH3 H CH(CH3)2 H
    58. H CH3 CH(CH3)2 H
    59. H H CH(CH3)2 CH3
    60. CH3 CH3 CH(CH3)2 H
    61. CH3 H CH(CH3)2 CH3
    62. H CH3 CH(CH3)2 CH3
    63. CH3 CH3 CH(CH3)2 CH3
    64. CH2CH(CH3)2 H H H
    65. CH2CH(CH3)2 CH3 H CH3
    66. CH2CH(CH3)2 H CH3 H
    67. CH2CH(CH3)2 H H CH3
    68. CH2CH(CH3)2 CH3 CH3 H
    69. CH2CH(CH3)2 CH3 H CH3
    70. CH2CH(CH3)2 H CH3 CH3
    71. CH2CH(CH3)2 CH3 CH3 CH3
    72. H CH2CH(CH3)2 H H
    73. CH3 CH2CH(CH3)2 H CH3
    74. H CH2CH(CH3)2 CH3 H
    75. H CH2CH(CH3)2 H CH3
    76. CH3 CH2CH(CH3)2 CH3 H
    77. CH3 CH2CH(CH3)2 H CH3
    78. H CH2CH(CH3)2 CH3 CH3
    79. CH3 CH2CH(CH3)2 CH3 CH3
    80. H H CH2CH(CH3)2 H
    81. CH3 H CH2CH(CH3)2 H
    82. H CH3 CH2CH(CH3)2 H
    83. H H CH2CH(CH3)2 CH3
    84. CH3 CH3 CH2CH(CH3)2 H
    85. CH3 H CH2CH(CH3)2 CH3
    86. H CH3 CH2CH(CH3)2 CH3
    87. CH3 CH3 CH2CH(CH3)2 CH3
    88. C(CH3)3 H H H
    89. C(CH3)3 CH3 H CH3
    90. C(CH3)3 H CH3 H
    91. C(CH3)3 H H CH3
    92. C(CH3)3 CH3 CH3 H
    93. C(CH3)3 CH3 H CH3
    94. C(CH3)3 H CH3 CH3
    95. C(CH3)3 CH3 CH3 CH3
    96. H C(CH3)3 H H
    97. CH3 C(CH3)3 H CH3
    98. H C(CH3)3 CH3 H
    99. H C(CH3)3 H CH3
    100. CH3 C(CH3)3 CH3 H
    101. CH3 C(CH3)3 H CH3
    102. H C(CH3)3 CH3 CH3
    103. CH3 C(CH3)3 CH3 CH3
    104. H H C(CH3)3 H
    105. CH3 H C(CH3)3 H
    106. H CH3 C(CH3)3 H
    107. H H C(CH3)3 CH3
    108. CH3 CH3 C(CH3)3 H
    109. CH3 H C(CH3)3 CH 3
    110. H CH3 C(CH3)3 CH3
    111. CH3 CH3 C(CH3)3 CH3
    112. CH2C(CH3)3 H H H
    113. CH2C(CH3)3 CH3 H CH3
    114. CH2C(CH3)3 H CH3 H
    115. CH2C(CH3)3 H H CH3
    116. CH2C(CH3)3 CH3 CH3 H
    117. CH2C(CH3)3 CH3 H CH3
    118. CH2C(CH3)3 H CH3 CH3
    119. CH2C(CH3)3 CH3 CH3 CH3
    120. H CH2C(CH3)3 H H
    121. CH3 CH2C(CH3)3 H CH3
    122. H CH2C(CH3)3 CH3 H
    123. H CH2C(CH3)3 H CH3
    124. CH3 CH2C(CH3)3 CH3 H
    125. CH3 CH2C(CH3)3 H CH 3
    126. H CH2C(CH3)3 CH3 CH3
    127. CH3 CH2C(CH3)3 CH3 CH3
    128. H H CH2C(CH3)3 H
    129. CH3 H CH2C(CH3)3 H
    130. H CH3 CH2C(CH3)3 H
    131. H H CH2C(CH3)3 CH3
    132. CH3 CH3 CH2C(CH3)3 H
    133. CH3 H CH2C(CH3)3 CH3
    134. H CH3 CH2C(CH3)3 CH 3
    135. CH3 CH3 CH2C(CH3)3 CH3
    136. CH2C(CH3)2CF3 H H H
    137. CH2C(CH3)2CF3 CH3 H CH3
    138. CH2C(CH3)2CF3 H CH3 H
    139. CH2C(CH3)2CF3 H H CH 3
    140. CH2C(CH3)2CF3 CH3 CH3 H
    141. CH2C(CH3)2CF3 CH3 H CH3
    142. CH2C(CH3)2CF3 H CH3 CH3
    143. CH2C(CH3)2CF3 CH3 CH3 CH3
    144. H CH2C(CH3)2CF3 H H
    145. CH3 CH2C(CH3)2CF3 H CH3
    146. H CH2C(CH3)2CF3 CH3 H
    147. H CH2C(CH3)2CF3 H CH3
    148. CH3 CH2C(CH3)2CF3 CH3 H
    149. CH3 CH2C(CH3)2CF3 H CH3
    150. H CH2C(CH3)2CF3 CH3 CH3
    151. CH3 CH2C(CH3)2CF3 CH3 CH3
    152. H H CH2C(CH3)2CF3 H
    153. CH3 H CH2C(CH3)2CF3 H
    154. H CH3 CH2C(CH3)2CF3 H
    155. H H CH2C((CH3)2CF3 CH3
    156. CH3 CH3 CH2C(CH3)2CF3 H
    157. CH3 H CH2C(CH3)2CF3 CH3
    158. H CH3 CH2C(CH3)2CF3 CH3
    159. CH3 CH3 CH2C(CH3)2CF3 CH3
    160. CH2CH2CF3 H H H
    161. CH2CH2CF3 CH3 H CH3
    162. CH2CH2CF3 H CH3 H
    163. CH2CH2CF3 H H CH 3
    164. CH2CH2CF3 CH3 CH3 H
    165. CH2CH2CF3 CH3 H CH3
    166. CH2CH2CF3 H CH3 CH3
    167. CH2CH2CF3 CH3 CH3 CH3
    168. H CH2CH2CF3 H H
    169. CH3 CH2CH2CF3 H CH3
    170. H CH2CH2CF3 CH3 H
    171. H CH2CH2CF3 H CH3
    172. CH3 CH2CH2CF3 CH3 H
    173. CH3 CH2CH2CF3 H CH3
    174. H CH2CH2CF3 CH3 CH3
    175. CH3 CH2CH2CF3 CH3 CH3
    176. H H CH2CH2CF3 H
    177. CH3 H CH2CH2CF3 H
    178. H CH3 CH2CH2CF3 H
    179. H H CH2CH2CF3 CH3
    180. CH3 CH3 CH2CH2CF3 H
    181. CH3 H CH2CH2CF3 CH3
    182. H CH3 CH2CH2CF3 CH3
    183. CH3 CH3 CH2CH2CF3 CH3
    184.
    Figure US20170324049A1-20171109-C00034
         		H H H
    185.
    Figure US20170324049A1-20171109-C00035
         		CH3 H CH3
    186.
    Figure US20170324049A1-20171109-C00036
         		H CH3 H
    187.
    Figure US20170324049A1-20171109-C00037
         		H H CH3
    188.
    Figure US20170324049A1-20171109-C00038
         		CH3 CH3 H
    189.
    Figure US20170324049A1-20171109-C00039
         		CH3 H CH3
    190.
    Figure US20170324049A1-20171109-C00040
         		H CH3 CH3
    191.
    Figure US20170324049A1-20171109-C00041
         		CH3 CH3 CH3
    192. H
    Figure US20170324049A1-20171109-C00042
         		H H
    193. CH3
    Figure US20170324049A1-20171109-C00043
         		H CH3
    194. H
    Figure US20170324049A1-20171109-C00044
         		CH3 H
    195. H
    Figure US20170324049A1-20171109-C00045
         		H CH3
    196. CH3
    Figure US20170324049A1-20171109-C00046
         		CH3 H
    197. CH3
    Figure US20170324049A1-20171109-C00047
         		H CH3
    198. H
    Figure US20170324049A1-20171109-C00048
         		CH3 CH3
    199. CH3
    Figure US20170324049A1-20171109-C00049
         		CH3 CH3
    200. H H
    Figure US20170324049A1-20171109-C00050
         		H
    201. CH3 H
    Figure US20170324049A1-20171109-C00051
         		H
    202. H CH3
    Figure US20170324049A1-20171109-C00052
         		H
    203. H H
    Figure US20170324049A1-20171109-C00053
         		CH3
    204. CH3 CH3
    Figure US20170324049A1-20171109-C00054
         		H
    205. CH3 H
    Figure US20170324049A1-20171109-C00055
         		CH3
    206. H CH3
    Figure US20170324049A1-20171109-C00056
         		CH3
    207. CH3 CH3
    Figure US20170324049A1-20171109-C00057
         		CH3
    208.
    Figure US20170324049A1-20171109-C00058
         		H H H
    209.
    Figure US20170324049A1-20171109-C00059
         		CH3 H CH3
    210.
    Figure US20170324049A1-20171109-C00060
         		H CH3 H
    211.
    Figure US20170324049A1-20171109-C00061
         		H H CH3
    212.
    Figure US20170324049A1-20171109-C00062
         		CH3 CH3 H
    213.
    Figure US20170324049A1-20171109-C00063
         		CH3 H CH3
    214.
    Figure US20170324049A1-20171109-C00064
         		H CH3 CH3
    215.
    Figure US20170324049A1-20171109-C00065
         		CH3 CH3 CH3
    216. H
    Figure US20170324049A1-20171109-C00066
         		H H
    217. CH3
    Figure US20170324049A1-20171109-C00067
         		H CH3
    218. H
    Figure US20170324049A1-20171109-C00068
         		CH3 H
    219. H
    Figure US20170324049A1-20171109-C00069
         		H CH 3
    220. CH3
    Figure US20170324049A1-20171109-C00070
         		CH3 H
    221. CH3
    Figure US20170324049A1-20171109-C00071
         		H CH3
    222. H
    Figure US20170324049A1-20171109-C00072
         		CH3 CH3
    223. CH3
    Figure US20170324049A1-20171109-C00073
         		CH3 CH3
    224. H H
    Figure US20170324049A1-20171109-C00074
         		H
    225. CH3 H
    Figure US20170324049A1-20171109-C00075
         		H
    226. H CH3
    Figure US20170324049A1-20171109-C00076
         		H
    227. H H
    Figure US20170324049A1-20171109-C00077
         		CH3
    228. CH3 CH3
    Figure US20170324049A1-20171109-C00078
         		H
    229. CH3 H
    Figure US20170324049A1-20171109-C00079
         		CH 3
    230. H CH3
    Figure US20170324049A1-20171109-C00080
         		CH3
    231. CH3 CH3
    Figure US20170324049A1-20171109-C00081
         		CH3
    232.
    Figure US20170324049A1-20171109-C00082
         		H H H
    233.
    Figure US20170324049A1-20171109-C00083
         		CH3 H CH3
    234.
    Figure US20170324049A1-20171109-C00084
         		H CH3 H
    235.
    Figure US20170324049A1-20171109-C00085
         		H H CH3
    236.
    Figure US20170324049A1-20171109-C00086
         		CH3 CH3 H
    237.
    Figure US20170324049A1-20171109-C00087
         		CH3 H CH3
    238.
    Figure US20170324049A1-20171109-C00088
         		H CH3 CH3
    239.
    Figure US20170324049A1-20171109-C00089
         		CH3 CH3 CH3
    240. H
    Figure US20170324049A1-20171109-C00090
         		H H
    241. CH3
    Figure US20170324049A1-20171109-C00091
         		H CH3
    242. H
    Figure US20170324049A1-20171109-C00092
         		CH3 H
    243. H
    Figure US20170324049A1-20171109-C00093
         		H CH3
    244. CH3
    Figure US20170324049A1-20171109-C00094
         		CH3 H
    245. CH3
    Figure US20170324049A1-20171109-C00095
         		H CH3
    246. H
    Figure US20170324049A1-20171109-C00096
         		CH3 CH3
    247. CH3
    Figure US20170324049A1-20171109-C00097
         		CH3 CH3
    248. H H
    Figure US20170324049A1-20171109-C00098
         		H
    249. CH3 H
    Figure US20170324049A1-20171109-C00099
         		H
    250. H CH3
    Figure US20170324049A1-20171109-C00100
         		H
    251. H H
    Figure US20170324049A1-20171109-C00101
         		CH3
    252. CH3 CH3
    Figure US20170324049A1-20171109-C00102
         		H
    253. CH3 H
    Figure US20170324049A1-20171109-C00103
         		CH3
    254. H CH3
    Figure US20170324049A1-20171109-C00104
         		CH3
    255. CH3 CH3
    Figure US20170324049A1-20171109-C00105
         		CH3
    256.
    Figure US20170324049A1-20171109-C00106
         		H H H
    257.
    Figure US20170324049A1-20171109-C00107
         		CH3 H CH3
    258.
    Figure US20170324049A1-20171109-C00108
         		H CH3 H
    259.
    Figure US20170324049A1-20171109-C00109
         		H H CH3
    260.
    Figure US20170324049A1-20171109-C00110
         		CH3 CH3 H
    261.
    Figure US20170324049A1-20171109-C00111
         		CH3 H CH3
    262.
    Figure US20170324049A1-20171109-C00112
         		H CH3 CH3
    263.
    Figure US20170324049A1-20171109-C00113
         		CH3 CH3 CH3
    264. H
    Figure US20170324049A1-20171109-C00114
         		H H
    265. CH3
    Figure US20170324049A1-20171109-C00115
         		H CH3
    266. H
    Figure US20170324049A1-20171109-C00116
         		CH3 H
    267. H
    Figure US20170324049A1-20171109-C00117
         		H CH3
    268. CH3
    Figure US20170324049A1-20171109-C00118
         		CH3 H
    269. CH3
    Figure US20170324049A1-20171109-C00119
         		H CH3
    270. H
    Figure US20170324049A1-20171109-C00120
         		CH3 CH3
    271. CH3
    Figure US20170324049A1-20171109-C00121
         		CH3 CH3
    272. H H
    Figure US20170324049A1-20171109-C00122
         		H
    273. CH3 H
    Figure US20170324049A1-20171109-C00123
         		H
    274. H CH3
    Figure US20170324049A1-20171109-C00124
         		H
    275. H H
    Figure US20170324049A1-20171109-C00125
         		CH3
    276. CH3 CH3
    Figure US20170324049A1-20171109-C00126
         		H
    277. CH3 H
    Figure US20170324049A1-20171109-C00127
         		CH3
    278. H CH3
    Figure US20170324049A1-20171109-C00128
         		CH3
    279. CH3 CH3
    Figure US20170324049A1-20171109-C00129
         		CH3
    280.
    Figure US20170324049A1-20171109-C00130
         		H H H
    281.
    Figure US20170324049A1-20171109-C00131
         		CH3 H CH3
    282.
    Figure US20170324049A1-20171109-C00132
         		H CH3 H
    283.
    Figure US20170324049A1-20171109-C00133
         		H H CH3
    284.
    Figure US20170324049A1-20171109-C00134
         		CH3 CH3 H
    285.
    Figure US20170324049A1-20171109-C00135
         		CH3 H CH3
    286.
    Figure US20170324049A1-20171109-C00136
         		H CH3 CH3
    287.
    Figure US20170324049A1-20171109-C00137
         		CH3 CH3 CH3
    288. H
    Figure US20170324049A1-20171109-C00138
         		H H
    289. CH3
    Figure US20170324049A1-20171109-C00139
         		H CH3
    290. H
    Figure US20170324049A1-20171109-C00140
         		CH3 H
    291. H
    Figure US20170324049A1-20171109-C00141
         		H CH3
    292. CH3
    Figure US20170324049A1-20171109-C00142
         		CH3 H
    293. CH3
    Figure US20170324049A1-20171109-C00143
         		H CH3
    294. H
    Figure US20170324049A1-20171109-C00144
         		CH3 CH3
    295. CH3
    Figure US20170324049A1-20171109-C00145
         		CH3 CH3
    296. H H
    Figure US20170324049A1-20171109-C00146
         		H
    297. CH3 H
    Figure US20170324049A1-20171109-C00147
         		H
    298. H CH3
    Figure US20170324049A1-20171109-C00148
         		H
    299. H H
    Figure US20170324049A1-20171109-C00149
         		CH3
    300. CH3 CH3
    Figure US20170324049A1-20171109-C00150
         		H
    301. CH3 H
    Figure US20170324049A1-20171109-C00151
         		CH3
    302. H CH3
    Figure US20170324049A1-20171109-C00152
         		CH3
    303. CH3 CH3
    Figure US20170324049A1-20171109-C00153
         		CH3
    304.
    Figure US20170324049A1-20171109-C00154
         		H H H
    305.
    Figure US20170324049A1-20171109-C00155
         		CH3 H CH3
    306.
    Figure US20170324049A1-20171109-C00156
         		H CH3 H
    307.
    Figure US20170324049A1-20171109-C00157
         		H H CH3
    308.
    Figure US20170324049A1-20171109-C00158
         		CH3 CH3 H
    309.
    Figure US20170324049A1-20171109-C00159
         		CH3 H CH3
    310.
    Figure US20170324049A1-20171109-C00160
         		H CH3 CH3
    311.
    Figure US20170324049A1-20171109-C00161
         		CH3 CH3 CH3
    312. H
    Figure US20170324049A1-20171109-C00162
         		H H
    313. CH3
    Figure US20170324049A1-20171109-C00163
         		H CH3
    314. H
    Figure US20170324049A1-20171109-C00164
         		CH3 H
    315. H
    Figure US20170324049A1-20171109-C00165
         		H CH3
    316. CH3
    Figure US20170324049A1-20171109-C00166
         		CH3 H
    317. CH3
    Figure US20170324049A1-20171109-C00167
         		H CH3
    318. H
    Figure US20170324049A1-20171109-C00168
         		CH3 CH3
    319. CH3
    Figure US20170324049A1-20171109-C00169
         		CH3 CH3
    320. H H
    Figure US20170324049A1-20171109-C00170
         		H
    321. CH3 H
    Figure US20170324049A1-20171109-C00171
         		H
    322. H CH3
    Figure US20170324049A1-20171109-C00172
         		H
    323. H H
    Figure US20170324049A1-20171109-C00173
         		CH3
    324. CH3 CH3
    Figure US20170324049A1-20171109-C00174
         		H
    325. CH3 H
    Figure US20170324049A1-20171109-C00175
         		CH3
    326. H CH3
    Figure US20170324049A1-20171109-C00176
         		CH3
    327. CH3 CH3
    Figure US20170324049A1-20171109-C00177
         		CH3
    328. CH(CH3)2 H CH2CH3 H
    329. CH(CH3)2 H CH(CH3)2 H
    330. CH(CH3)2 H CH2CH(CH3)2 H
    331. CH(CH3)2 H C(CH3)3 H
    332. CH(CH3)2 H CH2C(CH3)3 H
    333. CH(CH3)2 H CH2CH2CF3 H
    334. CH(CH3)2 H CH2C(CH3)2CF3 H
    335. CH(CH3)2 H
    Figure US20170324049A1-20171109-C00178
         		H
    336. CH(CH3)2 H
    Figure US20170324049A1-20171109-C00179
         		H
    337. CH(CH3)2 H
    Figure US20170324049A1-20171109-C00180
         		H
    338. CH(CH3)2 H
    Figure US20170324049A1-20171109-C00181
         		H
    339. CH(CH3)2 H
    Figure US20170324049A1-20171109-C00182
         		H
    340. CH(CH3)2 H
    Figure US20170324049A1-20171109-C00183
         		H
    341. C(CH3)3 H CH2CH3 H
    342. C(CH3)3 H CH(CH3)2 H
    343. C(CH3)3 H CH2CH(CH3)2 H
    344. C(CH3)3 H C(CH3)3 H
    345. C(CH3)3 H CH2C(CH3)3 H
    346. C(CH3)3 H CH2CH2CF3 H
    347. C(CH3)3 H CH2C(CH3)2CF3 H
    348. C(CH3)3 H
    Figure US20170324049A1-20171109-C00184
         		H
    349. C(CH3)3 H
    Figure US20170324049A1-20171109-C00185
         		H
    350. C(CH3)3 H
    Figure US20170324049A1-20171109-C00186
         		H
    351. C(CH3)3 H
    Figure US20170324049A1-20171109-C00187
         		H
    352. C(CH3)3 H
    Figure US20170324049A1-20171109-C00188
         		H
    353. C(CH3)3 H
    Figure US20170324049A1-20171109-C00189
         		H
    354. CH2C(CH3)3 H CH2CH3 H
    355. CH2C(CH3)3 H CH(CH3)2
    356. CH2C(CH3)3 H CH2CH(CH3)2 H
    357. CH2C(CH3)3 H C(CH3)3 H
    358. CH2C(CH3)3 H CH2C(CH3)3 H
    359. CH2C(CH3)3 H CH2CH2CF3 H
    360. CH2C(CH3)3 H CH2C(CH3)2CF3 H
    361. CH2C(CH3)3 H
    Figure US20170324049A1-20171109-C00190
         		H
    362. CH2C(CH3)3 H
    Figure US20170324049A1-20171109-C00191
         		H
    363. CH2C(CH3)3 H
    Figure US20170324049A1-20171109-C00192
         		H
    364. CH2C(CH3)3 H
    Figure US20170324049A1-20171109-C00193
         		H
    365. CH2C(CH3)3 H
    Figure US20170324049A1-20171109-C00194
         		H
    366. CH2C(CH3)3 H
    Figure US20170324049A1-20171109-C00195
         		H
    367.
    Figure US20170324049A1-20171109-C00196
         		H CH2CH3 H
    368.
    Figure US20170324049A1-20171109-C00197
         		H CH(CH3)2 H
    369.
    Figure US20170324049A1-20171109-C00198
         		H CH2CH(CH3)2 H
    370.
    Figure US20170324049A1-20171109-C00199
         		H C(CH3)3
    371.
    Figure US20170324049A1-20171109-C00200
         		H CH2C(CH3)3 H
    372.
    Figure US20170324049A1-20171109-C00201
         		H CH2CH2CF3 H
    373.
    Figure US20170324049A1-20171109-C00202
         		H CH2C(CH3)2CF3 H
    374.
    Figure US20170324049A1-20171109-C00203
         		H
    Figure US20170324049A1-20171109-C00204
         		H
    375.
    Figure US20170324049A1-20171109-C00205
         		H
    Figure US20170324049A1-20171109-C00206
         		H
    376.
    Figure US20170324049A1-20171109-C00207
         		H
    Figure US20170324049A1-20171109-C00208
         		H
    377.
    Figure US20170324049A1-20171109-C00209
         		H
    Figure US20170324049A1-20171109-C00210
         		H
    378.
    Figure US20170324049A1-20171109-C00211
         		H
    Figure US20170324049A1-20171109-C00212
         		H
    379.
    Figure US20170324049A1-20171109-C00213
         		H
    Figure US20170324049A1-20171109-C00214
         		H
    380.
    Figure US20170324049A1-20171109-C00215
         		H CH2CH3 H
    381.
    Figure US20170324049A1-20171109-C00216
         		H CH(CH3)2 H
    382.
    Figure US20170324049A1-20171109-C00217
         		H CH2CH(CH3)2 H
    383.
    Figure US20170324049A1-20171109-C00218
         		H C(CH3)3 H
    384.
    Figure US20170324049A1-20171109-C00219
         		H CH2C(CH3)3 H
    385.
    Figure US20170324049A1-20171109-C00220
         		H CH2CH2CF3 H
    386.
    Figure US20170324049A1-20171109-C00221
         		H CH2C(CH3)2CF3 H
    387.
    Figure US20170324049A1-20171109-C00222
         		H
    Figure US20170324049A1-20171109-C00223
         		H
    388.
    Figure US20170324049A1-20171109-C00224
         		H
    Figure US20170324049A1-20171109-C00225
         		H
    389.
    Figure US20170324049A1-20171109-C00226
         		H
    Figure US20170324049A1-20171109-C00227
         		H
    390.
    Figure US20170324049A1-20171109-C00228
         		H
    Figure US20170324049A1-20171109-C00229
         		H
    391.
    Figure US20170324049A1-20171109-C00230
         		H
    Figure US20170324049A1-20171109-C00231
         		H
    392.
    Figure US20170324049A1-20171109-C00232
         		H
    Figure US20170324049A1-20171109-C00233
         		H
    393.
    Figure US20170324049A1-20171109-C00234
         		H CH2CH(CH3)2 H
    394.
    Figure US20170324049A1-20171109-C00235
         		H C(CH3)3 H
    395.
    Figure US20170324049A1-20171109-C00236
         		H CH2C(CH3)3 H
    396.
    Figure US20170324049A1-20171109-C00237
         		H CH2CH2CF3 H
    397.
    Figure US20170324049A1-20171109-C00238
         		H CH2C(CH3)2CF3 H
    398.
    Figure US20170324049A1-20171109-C00239
         		H
    Figure US20170324049A1-20171109-C00240
         		H
    399.
    Figure US20170324049A1-20171109-C00241
         		H
    Figure US20170324049A1-20171109-C00242
         		H
    400.
    Figure US20170324049A1-20171109-C00243
         		H
    Figure US20170324049A1-20171109-C00244
         		H
    401.
    Figure US20170324049A1-20171109-C00245
         		H
    Figure US20170324049A1-20171109-C00246
         		H
    402.
    Figure US20170324049A1-20171109-C00247
         		H
    Figure US20170324049A1-20171109-C00248
         		H
    403.
    Figure US20170324049A1-20171109-C00249
         		H
    Figure US20170324049A1-20171109-C00250
         		H
    404.
    Figure US20170324049A1-20171109-C00251
         		H CH2CH(CH3)2 H
    405.
    Figure US20170324049A1-20171109-C00252
         		H C(CH3)3 H
    406.
    Figure US20170324049A1-20171109-C00253
         		H CH2C(CH3)3 H
    407.
    Figure US20170324049A1-20171109-C00254
         		H CH2CH2CF3 H
    408.
    Figure US20170324049A1-20171109-C00255
         		H CH2C(CH3)2CF3 H
    409.
    Figure US20170324049A1-20171109-C00256
         		H
    Figure US20170324049A1-20171109-C00257
         		H
    410.
    Figure US20170324049A1-20171109-C00258
         		H
    Figure US20170324049A1-20171109-C00259
         		H
    411.
    Figure US20170324049A1-20171109-C00260
         		H
    Figure US20170324049A1-20171109-C00261
         		H
    412.
    Figure US20170324049A1-20171109-C00262
         		H
    Figure US20170324049A1-20171109-C00263
         		H
    413.
    Figure US20170324049A1-20171109-C00264
         		H
    Figure US20170324049A1-20171109-C00265
         		H
    414.
    Figure US20170324049A1-20171109-C00266
         		H
    Figure US20170324049A1-20171109-C00267
         		H
    415.
    Figure US20170324049A1-20171109-C00268
         		H CH2CH(CH3)2 H
    416.
    Figure US20170324049A1-20171109-C00269
         		H C(CH3)3 H
    417.
    Figure US20170324049A1-20171109-C00270
         		H CH2C(CH3)3 H
    418.
    Figure US20170324049A1-20171109-C00271
         		H CH2CH2CF3 H
    419.
    Figure US20170324049A1-20171109-C00272
         		H CH2C(CH3)2CF3 H
    420.
    Figure US20170324049A1-20171109-C00273
         		H
    Figure US20170324049A1-20171109-C00274
         		H
    421.
    Figure US20170324049A1-20171109-C00275
         		H
    Figure US20170324049A1-20171109-C00276
         		H
    422.
    Figure US20170324049A1-20171109-C00277
         		H
    Figure US20170324049A1-20171109-C00278
         		H
    423.
    Figure US20170324049A1-20171109-C00279
         		H
    Figure US20170324049A1-20171109-C00280
         		H
    424.
    Figure US20170324049A1-20171109-C00281
         		H
    Figure US20170324049A1-20171109-C00282
         		H
    425.
    Figure US20170324049A1-20171109-C00283
         		H
    Figure US20170324049A1-20171109-C00284
         		H
    426. H H H H
    427. CD3 H H H
    428. H CD3 H H
    429. H H CD3 H
    430. H H H CD3
    431. CD3 H CD3 H
    432. CD3 H H CD3
    433. H CD3 CH3 H
    434. H CD3 H CD3
    435. H H CD3 CD3
    436. CD3 CD3 CD3 H
    437. CD3 CD3 H CD3
    438. CD3 H CD3 CD3
    439. H CD3 CD3 CD3
    440. CD3 CD3 CD3 CD3
    441. CD2CH3 H H H
    442. CD2CH3 CD3 H CD3
    443. CD2CH3 H CD3 H
    444. CD2CH3 H H CD3
    445. CD2CH3 CD3 CD3 H
    446. CD2CH3 CD3 H CD3
    447. CD2CH3 H CD3 CD3
    448. CD2CH3 CD3 CD3 CD3
    449. H CD2CH3 H H
    450. CH3 CD2CH3 H CD3
    451. H CD2CH3 CD3 H
    452. H CD2CH3 H CD3
    453. CD3 CD2CH3 CD3 H
    454. CD3 CD2CH3 H CD3
    455. H CD2CH3 CD3 CD3
    456. CD3 CD2CH3 CD3 CD3
    457. H H CD2CH3 H
    458. CD3 H CD2CH3 H
    459. H CD3 CD2CH3 H
    460. H H CD2CH3 CD3
    461. CD3 CD3 CD2CH3 H
    462. CD3 H CD2CH3 CD3
    463. H CD3 CD2CH3 CD3
    464. CD3 CD3 CD2CH3 CD3
    465. CD(CH3)2 H H H
    466. CD(CH3)2 CD3 H CD3
    467. CD(CH3)2 H CD3 H
    468. CD(CH3)2 H H CD3
    469. CD(CH3)2 CD3 CD3 H
    470. CD(CH3)2 CD3 H CD3
    471. CD(CH3)2 H CD3 CD3
    472. CD(CH3)2 CD3 CD3 CD3
    473. H CD(CH3)2 H H
    474. CD3 CD(CH3)2 H CD3
    475. H CD(CH3)2 CD3 H
    476. H CD(CH3)2 H CD3
    477. CD3 CD(CH3)2 CD3 H
    478. CD3 CD(CH3)2 H CD3
    479. H CD(CH3)2 CD3 CD3
    480. CD3 CD(CH3)2 CD3 CD3
    481. H H CD(CH3)2 H
    482. CD3 H CD(CH3)2 H
    483. H CD3 CD(CH3)2 H
    484. H H CD(CH3)2 CD3
    485. CD3 CD3 CD(CH3)2 H
    486. CD3 H CD(CH3)2 CD3
    487. H CD3 CD(CH3)2 CD3
    488. CD3 CD3 CD(CH3)2 CD3
    489. CD(CD3)2 H H H
    490. CD(CD3)2 CD3 H CD3
    491. CD(CD3)2 H CD3 H
    492. CD(CD3)2 H H CD3
    493. CD(CD3)2 CD3 CD3 H
    494. CD(CD3)2 CD3 H CD3
    495. CD(CD3)2 H CD3 CD3
    496. CD(CD3)2 CD3 CD3 CD3
    497. H CD(CD3)2 H H
    498. CH3 CD(CD3)2 H CD3
    499. H CD(CD3)2 CD3 H
    500. H CD(CD3)2 H CD3
    501. CD3 CD(CD3)2 CD3 H
    502. CD3 CD(CD3)2 H CD3
    503. H CD(CD3)2 CD3 CD3
    504. CD3 CD(CD3)2 CD3 CD3
    505. H H CD(CD3)2 H
    506. CD3 H CD(CD3)2 H
    507. H CD3 CD(CD3)2 H
    508. H H CD(CD3)2 CD3
    509. CD3 CD3 CD(CD3)2 H
    510. CD3 H CD(CD3)2 CD3
    511. H CD3 CD(CD3)2 CD3
    512. CD3 CD3 CD(CD3)2 CD3
    513. CD2CH(CH3)2 H H H
    514. CD2CH(CH3)2 CD3 H CD3
    515. CD2CH(CH3)2 H CD3 H
    516. CD2CH(CH3)2 H H CD3
    517. CD2CH(CH3)2 CD3 CD3 H
    518. CD2CH(CH3)2 CD3 H CD3
    519. CD2CH(CH3)2 H CD3 CD3
    520. CD2CH(CH3)2 CD3 CD3 CD3
    521. H CD2CH(CH3)2 H H
    522. CD3 CD2CH(CH3)2 H CD3
    523. H CD2CH(CH3)2 CD3 H
    524. H CD2CH(CH3)2 H CD3
    525. CD3 CD2CH(CH3)2 CD3 H
    526. CD3 CD2CH(CH3)2 H CD3
    527. H CD2CH(CH3)2 CD3 CD3
    528. CD3 CD2CH(CH3)2 CD3 CD3
    529. H H CD2CH(CH3)2 H
    530. CD3 H CD2CH(CH3)2 H
    531. H CD3 CD2CH(CH3)2 H
    532. H H CD2CH(CH3)2 CD3
    533. CD3 CD3 CD2CH(CH3)2 H
    534. CD3 H CD2CH(CH3)2 CD3
    535. H CD3 CD2CH(CH3)2 CD3
    536. CD3 CD3 CD2CH(CH3)2 CD3
    537. CD2C(CH3)3 H H H
    538. CD2C(CH3)3 CD3 H CD3
    539. CD2C(CH3)3 H CD3 H
    540. CD2C(CH3)3 H H CD3
    541. CD2C(CH3)3 CD3 CD3 H
    542. CD2C(CH3)3 CD3 H CD3
    543. CD2C(CH3)3 H CD3 CD3
    544. CD2C(CH3)3 CH3 CD3 CD3
    545. H CD2C(CH3)3 H H
    546. CD3 CD2C(CH3)3 H CD3
    547. H CD2C(CH3)3 CD3 H
    548. H CD2C(CH3)3 H CD3
    549. CD CD2C(CH3)3 CD3 H
    550. CD3 CD2C(CH3)3 H CD3
    551. H CD2C(CH3)3 CD3 CD3
    552. CD3 CD2C(CH3)3 CD3 CD3
    553. H H CD2C(CH3)3 H
    554. CD3 H CD2C(CH3)3 H
    555. H CD3 CD2C(CH3)3 H
    556. H H CD2C(CH3)3 CD3
    557. CD3 CD3 CD2C(CH3)3 H
    558. CD3 H CD2C(CH3)3 CD3
    559. H CD3 CD2C(CH3)3 CD3
    560. CD3 CD3 CD2C(CH3)3 CD3
    561. CD2C(CH3)2CF3 H H H
    562. CD2C(CH3)2CF3 CD3 H CD3
    563. CD2C(CH3)2CF3 H CD3 H
    564. CD2C(CH3)2CF3 H H CD3
    565. CD2C(CH3)2CF3 CD3 CD3 H
    566. CD2C(CH3)2CF3 CD3 H CD3
    567. CD2C(CH3)2CF3 H CD3 CD3
    568. CD2C(CH3)2CF3 CD3 CD3 CD3
    569. H CD2C(CH3)2CF3 H H
    570. CD3 CD2C(CH3)2CF3 H CD3
    571. H CD2C(CH3)2CF3 CD3 H
    572. H CD2C(CH3)2CF3 H CD3
    573. CD3 CD2C(CH3)2CF3 CD3 H
    574. CD3 CD2C(CH3)2CF3 H CD3
    575. H CD2C(CH3)2CF3 CD3 CD3
    576. CD3 CD2C(CH3)2CF3 CD3 CD3
    577. H H CD2C(CH3)2CF3 H
    578. CD3 H CD2C(CH3)2CF3 H
    579. H CD3 CD2C(CH3)2CF3 H
    580. H H CD2C(CH3)2CF3 CD3
    581. CD3 CD3 CD2C(CH3)2CF3 H
    582. CD3 H CD2C(CH3)2CF3 CD3
    583. H CD3 CD2C(CH3)2CF3 CD3
    584. CD3 CD3 CD2C(CH3)2CF3 CD3
    585. CD2CH2CF3 H H H
    586. CD2CH2CF3 CD3 H CD3
    587. CD2CH2CF3 H CD3 H
    588. CD2CH2CF3 H H CD3
    589. CD2CH2CF3 CD3 CD3 H
    590. CD2CH2CF3 CD3 H CD3
    591. CD2CH2CF3 H CD3 CD3
    592. CD2CH2CF3 CD3 CD3 CD3
    593. H CD2CH2CF3 H H
    594. CD3 CD2CH2CF3 H CD3
    595. H CD2CH2CF3 CD3 H
    596. H CD2CH2CF3 H CD3
    597. CD3 CD2CH2CF3 CD3 H
    598. CD3 CD2CH2CF3 H CD3
    599. H CD2CH2CF3 CD3 CD3
    600. CD3 CD2CH2CF3 CD3 CD3
    601. H H CD2CH2CF3 H
    602. CD3 H CD2CH2CF3 H
    603. H CD3 CD2CH2CF3 H
    604. H H CD2CH2CF3 CD3
    605. CD3 CD3 CD2CH2CF3 H
    606. CD3 H CD2CH2CF3 CD3
    607. H CD3 CD2CH2CF3 CD3
    608. CD3 CD3 CD2CH2CF3 CD3
    609.
    Figure US20170324049A1-20171109-C00285
         		H H H
    610.
    Figure US20170324049A1-20171109-C00286
         		CD3 H CD3
    611.
    Figure US20170324049A1-20171109-C00287
         		H CD3 H
    612.
    Figure US20170324049A1-20171109-C00288
         		H H CD3
    613.
    Figure US20170324049A1-20171109-C00289
         		CD3 CD3 H
    614.
    Figure US20170324049A1-20171109-C00290
         		CD3 H CD3
    615.
    Figure US20170324049A1-20171109-C00291
         		H CD3 CD3
    616.
    Figure US20170324049A1-20171109-C00292
         		CD3 CD3 CD3
    617. H
    Figure US20170324049A1-20171109-C00293
         		H H
    618. CD3
    Figure US20170324049A1-20171109-C00294
         		H CD3
    619. H
    Figure US20170324049A1-20171109-C00295
         		CD3 H
    620. H
    Figure US20170324049A1-20171109-C00296
         		H CD3
    621. CD3
    Figure US20170324049A1-20171109-C00297
         		CD3 H
    622. CD3
    Figure US20170324049A1-20171109-C00298
         		H CD3
    623. H
    Figure US20170324049A1-20171109-C00299
         		CD3 CD3
    624. CD3
    Figure US20170324049A1-20171109-C00300
         		CD3 CD3
    625. H H
    Figure US20170324049A1-20171109-C00301
         		H
    626. CD3 H
    Figure US20170324049A1-20171109-C00302
         		H
    627. H CD3
    Figure US20170324049A1-20171109-C00303
         		H
    628. H H
    Figure US20170324049A1-20171109-C00304
         		CD3
    629. CD3 CD3
    Figure US20170324049A1-20171109-C00305
         		H
    630. CD3 H
    Figure US20170324049A1-20171109-C00306
         		CD3
    631. H CD3
    Figure US20170324049A1-20171109-C00307
         		CD3
    632. CD3 CD3
    Figure US20170324049A1-20171109-C00308
         		CD3
    633.
    Figure US20170324049A1-20171109-C00309
         		H H H
    634.
    Figure US20170324049A1-20171109-C00310
         		CD3 H CD3
    635.
    Figure US20170324049A1-20171109-C00311
         		H CD3 H
    636.
    Figure US20170324049A1-20171109-C00312
         		H H CD3
    637.
    Figure US20170324049A1-20171109-C00313
         		CD3 CD3 H
    638.
    Figure US20170324049A1-20171109-C00314
         		CD3 H CD3
    639.
    Figure US20170324049A1-20171109-C00315
         		H CD3 CD3
    640.
    Figure US20170324049A1-20171109-C00316
         		CD3 CD3 CD3
    641. H
    Figure US20170324049A1-20171109-C00317
         		H H
    642. CH3
    Figure US20170324049A1-20171109-C00318
         		H CD3
    643. H
    Figure US20170324049A1-20171109-C00319
         		CD3 H
    644. H
    Figure US20170324049A1-20171109-C00320
         		H CD3
    645. CD3
    Figure US20170324049A1-20171109-C00321
         		CD3 H
    646. CD3
    Figure US20170324049A1-20171109-C00322
         		H CD3
    647. H
    Figure US20170324049A1-20171109-C00323
         		CD3 CD3
    648. CH3
    Figure US20170324049A1-20171109-C00324
         		CD3 CD3
    649. H H
    Figure US20170324049A1-20171109-C00325
         		H
    650. CD3 H
    Figure US20170324049A1-20171109-C00326
         		H
    651. H CD3
    Figure US20170324049A1-20171109-C00327
         		H
    652. H H
    Figure US20170324049A1-20171109-C00328
         		CD3
    653. CD3 CD3
    Figure US20170324049A1-20171109-C00329
         		H
    654. CD3 H
    Figure US20170324049A1-20171109-C00330
         		CD3
    655. H CD3
    Figure US20170324049A1-20171109-C00331
         		CD3
    656. CD3 CD3
    Figure US20170324049A1-20171109-C00332
         		CD3
    657.
    Figure US20170324049A1-20171109-C00333
         		H H H
    658.
    Figure US20170324049A1-20171109-C00334
         		CD3 H CD3
    659.
    Figure US20170324049A1-20171109-C00335
         		H CD3 H
    660.
    Figure US20170324049A1-20171109-C00336
         		H H CD3
    661.
    Figure US20170324049A1-20171109-C00337
         		CD3 CD3 H
    662.
    Figure US20170324049A1-20171109-C00338
         		CD3 H CD3
    663.
    Figure US20170324049A1-20171109-C00339
         		H CD3 CD3
    664.
    Figure US20170324049A1-20171109-C00340
         		CD3 CD3 CD3
    665. H
    Figure US20170324049A1-20171109-C00341
         		H H
    666. CD3
    Figure US20170324049A1-20171109-C00342
         		H CD3
    667. H
    Figure US20170324049A1-20171109-C00343
         		CD3 H
    668. H
    Figure US20170324049A1-20171109-C00344
         		H CD3
    669. CD3
    Figure US20170324049A1-20171109-C00345
         		CD3 H
    670. CD3
    Figure US20170324049A1-20171109-C00346
         		H CD3
    671. H
    Figure US20170324049A1-20171109-C00347
         		CD3 CD3
    672. CD3
    Figure US20170324049A1-20171109-C00348
         		CD3 CD3
    673. H H
    Figure US20170324049A1-20171109-C00349
         		H
    674. CD3 H
    Figure US20170324049A1-20171109-C00350
         		H
    675. H CD3
    Figure US20170324049A1-20171109-C00351
         		H
    676. H H
    Figure US20170324049A1-20171109-C00352
         		CD3
    677. CD3 CD3
    Figure US20170324049A1-20171109-C00353
         		H
    678. CD3 H
    Figure US20170324049A1-20171109-C00354
         		CD3
    679. H CD3
    Figure US20170324049A1-20171109-C00355
         		CD3
    680. CD3 CD3
    Figure US20170324049A1-20171109-C00356
         		CD3
    681.
    Figure US20170324049A1-20171109-C00357
         		H H H
    682.
    Figure US20170324049A1-20171109-C00358
         		CD3 H CD3
    683.
    Figure US20170324049A1-20171109-C00359
         		H CD3 H
    684.
    Figure US20170324049A1-20171109-C00360
         		H H CD3
    685.
    Figure US20170324049A1-20171109-C00361
         		CD3 CD3 H
    686.
    Figure US20170324049A1-20171109-C00362
         		CD3 H CD3
    687.
    Figure US20170324049A1-20171109-C00363
         		H CD3 CD3
    688.
    Figure US20170324049A1-20171109-C00364
         		CD3 CD3 CD3
    689. H
    Figure US20170324049A1-20171109-C00365
         		H H
    690. CD3
    Figure US20170324049A1-20171109-C00366
         		H CD3
    691. H
    Figure US20170324049A1-20171109-C00367
         		CD3 H
    692. H
    Figure US20170324049A1-20171109-C00368
         		H CD3
    693. CD3
    Figure US20170324049A1-20171109-C00369
         		CD3 H
    694. CD3
    Figure US20170324049A1-20171109-C00370
         		H CD3
    695. H
    Figure US20170324049A1-20171109-C00371
         		CD3 CD3
    696. CD3
    Figure US20170324049A1-20171109-C00372
         		CD3 CD3
    697. H H
    Figure US20170324049A1-20171109-C00373
         		H
    698. CD3 H
    Figure US20170324049A1-20171109-C00374
         		H
    699. H CD3
    Figure US20170324049A1-20171109-C00375
         		H
    700. H H
    Figure US20170324049A1-20171109-C00376
         		CD3
    701. CD3 CD3
    Figure US20170324049A1-20171109-C00377
         		H
    702. CD3 H
    Figure US20170324049A1-20171109-C00378
         		CD3
    703. H CD3
    Figure US20170324049A1-20171109-C00379
         		CD3
    704. CD3 CD3
    Figure US20170324049A1-20171109-C00380
         		CD3
    705.
    Figure US20170324049A1-20171109-C00381
         		H H H
    706.
    Figure US20170324049A1-20171109-C00382
         		CD3 H CD3
    707.
    Figure US20170324049A1-20171109-C00383
         		H CD3 H
    708.
    Figure US20170324049A1-20171109-C00384
         		H H CD3
    709.
    Figure US20170324049A1-20171109-C00385
         		CD3 CD3 H
    710.
    Figure US20170324049A1-20171109-C00386
         		CD3 H CD3
    711.
    Figure US20170324049A1-20171109-C00387
         		H CD3 CD3
    712.
    Figure US20170324049A1-20171109-C00388
         		CD3 CD3 CD3
    713. H
    Figure US20170324049A1-20171109-C00389
         		H H
    714. CD3
    Figure US20170324049A1-20171109-C00390
         		H CD3
    715. H
    Figure US20170324049A1-20171109-C00391
         		CD3 H
    716. H
    Figure US20170324049A1-20171109-C00392
         		H CD3
    717. CD3
    Figure US20170324049A1-20171109-C00393
         		CD3 H
    718. CD3
    Figure US20170324049A1-20171109-C00394
         		H CD3
    719. H
    Figure US20170324049A1-20171109-C00395
         		CD3 CD3
    720. CD3
    Figure US20170324049A1-20171109-C00396
         		CD3 CD3
    721. H H
    Figure US20170324049A1-20171109-C00397
         		H
    722. CD3 H
    Figure US20170324049A1-20171109-C00398
         		H
    723. H CD3
    Figure US20170324049A1-20171109-C00399
         		H
    724. H H
    Figure US20170324049A1-20171109-C00400
         		CD3
    725. CD3 CD3
    Figure US20170324049A1-20171109-C00401
         		H
    726. CD3 H
    Figure US20170324049A1-20171109-C00402
         		CD3
    727. H CD3
    Figure US20170324049A1-20171109-C00403
         		CD3
    728. CD3 CD3
    Figure US20170324049A1-20171109-C00404
         		CD3
    729.
    Figure US20170324049A1-20171109-C00405
         		H H H
    730.
    Figure US20170324049A1-20171109-C00406
         		CD3 H CD3
    731.
    Figure US20170324049A1-20171109-C00407
         		H CD3 H
    732.
    Figure US20170324049A1-20171109-C00408
         		H H CD3
    733.
    Figure US20170324049A1-20171109-C00409
         		CH3 CH3 H
    734.
    Figure US20170324049A1-20171109-C00410
         		CD3 H CD3
    735.
    Figure US20170324049A1-20171109-C00411
         		H CD3 CD3
    736.
    Figure US20170324049A1-20171109-C00412
         		CD3 CD3 CD3
    737. H
    Figure US20170324049A1-20171109-C00413
         		H H
    738. CD3
    Figure US20170324049A1-20171109-C00414
         		H CD3
    739. H
    Figure US20170324049A1-20171109-C00415
         		CD3 H
    740. H
    Figure US20170324049A1-20171109-C00416
         		H CD3
    741. CD3
    Figure US20170324049A1-20171109-C00417
         		CD3 H
    742. CD3
    Figure US20170324049A1-20171109-C00418
         		H CD3
    743. H
    Figure US20170324049A1-20171109-C00419
         		CD3 CD3
    744. CD3
    Figure US20170324049A1-20171109-C00420
         		CD3 CD3
    745. H H
    Figure US20170324049A1-20171109-C00421
         		H
    746. CD3 H
    Figure US20170324049A1-20171109-C00422
         		H
    747. H CD3
    Figure US20170324049A1-20171109-C00423
         		H
    748. H H
    Figure US20170324049A1-20171109-C00424
         		CH3
    749. CD3 CD3
    Figure US20170324049A1-20171109-C00425
         		H
    750. CD3 H
    Figure US20170324049A1-20171109-C00426
         		CD3
    751. H CD3
    Figure US20170324049A1-20171109-C00427
         		CD3
    752. CD3 CD3
    Figure US20170324049A1-20171109-C00428
         		CD3
    753. CD(CH3)2 H CD2CH3 H
    754. CD(CH3)2 H CD(CH3)2 H
    755. CD(CH3)2 H CD2CH(CH3)2 H
    756. CD(CH3)2 H C(CH3)3 H
    757. CD(CH3)2 H CD2C(CH3)3 H
    758. CD(CH3)2 H CD2CH2CF3 H
    759. CD(CH3)2 H CD2C(CH3)2CF3 H
    760. CD(CH3)2 H
    Figure US20170324049A1-20171109-C00429
         		H
    761. CD(CH3)2 H
    Figure US20170324049A1-20171109-C00430
         		H
    762. CD(CH3)2 H
    Figure US20170324049A1-20171109-C00431
         		H
    763. CD(CH3)2 H
    Figure US20170324049A1-20171109-C00432
         		H
    764. CD(CH3)2 H
    Figure US20170324049A1-20171109-C00433
         		H
    765. CD(CH3)2 H
    Figure US20170324049A1-20171109-C00434
         		H
    766. C(CH3)3 H CD2CH3 H
    767. C(CH3)3 H CD(CH3)2 H
    768. C(CH3)3 H CD2CH(CH3)2 H
    769. C(CH3)3 H C(CH3)3 H
    770. C(CH3)3 H CD2C(CH3)3 H
    771. C(CH3)3 H CD2CH2CF3 H
    772. C(CH3)3 H CD2C(CH3)2CF3 H
    773. C(CH3)3 H
    Figure US20170324049A1-20171109-C00435
         		H
    774. C(CH3)3 H
    Figure US20170324049A1-20171109-C00436
         		H
    775. C(CH3)3 H
    Figure US20170324049A1-20171109-C00437
         		H
    776. C(CH3)3 H
    Figure US20170324049A1-20171109-C00438
         		H
    777. C(CH3)3 H
    Figure US20170324049A1-20171109-C00439
         		H
    778. C(CH3)3 H
    Figure US20170324049A1-20171109-C00440
         		H
    779. CD2C(CH3)3 H CD2CH3 H
    780. CD2C(CH3)3 H CD(CH3)2 H
    781. CD2C(CH3)3 H CD2CH(CH3)2 H
    782. CD2C(CH3)3 H C(CH3)3 H
    783. CD2C(CH3)3 H CD2C(CH3)3 H
    784. CD2C(CH3)3 H CD2CH2CF3 H
    785. CD2C(CH3)3 H CD2C(CH3)2CF3 H
    786. CD2C(CH3)3 H
    Figure US20170324049A1-20171109-C00441
         		H
    787. CD2C(CH3)3 H
    Figure US20170324049A1-20171109-C00442
         		H
    788. CD2C(CH3)3 H
    Figure US20170324049A1-20171109-C00443
         		H
    789. CD2C(CH3)3 H
    Figure US20170324049A1-20171109-C00444
         		H
    790. CD2C(CH3)3 H
    Figure US20170324049A1-20171109-C00445
         		H
    791. CD2C(CH3)3 H
    Figure US20170324049A1-20171109-C00446
         		H
    792.
    Figure US20170324049A1-20171109-C00447
         		H CD2CH3 H
    793.
    Figure US20170324049A1-20171109-C00448
         		H CD(CH3)2 H
    794.
    Figure US20170324049A1-20171109-C00449
         		H CD2CH(CH3)2 H
    795.
    Figure US20170324049A1-20171109-C00450
         		H C(CH3)3 H
    796.
    Figure US20170324049A1-20171109-C00451
         		H CD2C(CH3)3 H
    797.
    Figure US20170324049A1-20171109-C00452
         		H CD2CH2CF3 H
    798.
    Figure US20170324049A1-20171109-C00453
         		H CD2C(CH3)2CF3 H
    799.
    Figure US20170324049A1-20171109-C00454
         		H
    Figure US20170324049A1-20171109-C00455
         		H
    800.
    Figure US20170324049A1-20171109-C00456
         		H
    Figure US20170324049A1-20171109-C00457
         		H
    801.
    Figure US20170324049A1-20171109-C00458
         		H
    Figure US20170324049A1-20171109-C00459
         		H
    802.
    Figure US20170324049A1-20171109-C00460
         		H
    Figure US20170324049A1-20171109-C00461
         		H
    803.
    Figure US20170324049A1-20171109-C00462
         		H
    Figure US20170324049A1-20171109-C00463
         		H
    804.
    Figure US20170324049A1-20171109-C00464
         		H
    Figure US20170324049A1-20171109-C00465
         		H
    805.
    Figure US20170324049A1-20171109-C00466
         		H CD2CH3 H
    806.
    Figure US20170324049A1-20171109-C00467
         		H CD(CH3)2 H
    807.
    Figure US20170324049A1-20171109-C00468
         		H CD2CH(CH3)2 H
    808.
    Figure US20170324049A1-20171109-C00469
         		H C(CH3)3 H
    809.
    Figure US20170324049A1-20171109-C00470
         		H CD2C(CH3)3 H
    810.
    Figure US20170324049A1-20171109-C00471
         		H CD2CH2CF3 H
    811.
    Figure US20170324049A1-20171109-C00472
         		H CD2C(CH3)2CF3 H
    812.
    Figure US20170324049A1-20171109-C00473
         		H
    Figure US20170324049A1-20171109-C00474
         		H
    813.
    Figure US20170324049A1-20171109-C00475
         		H
    Figure US20170324049A1-20171109-C00476
         		H
    814.
    Figure US20170324049A1-20171109-C00477
         		H
    Figure US20170324049A1-20171109-C00478
         		H
    815.
    Figure US20170324049A1-20171109-C00479
         		H
    Figure US20170324049A1-20171109-C00480
         		H
    816.
    Figure US20170324049A1-20171109-C00481
         		H
    Figure US20170324049A1-20171109-C00482
         		H
    817.
    Figure US20170324049A1-20171109-C00483
         		H
    Figure US20170324049A1-20171109-C00484
         		H
    818.
    Figure US20170324049A1-20171109-C00485
         		H CD2CH3 H
    819.
    Figure US20170324049A1-20171109-C00486
         		H CD(CH3)2 H
    820.
    Figure US20170324049A1-20171109-C00487
         		H CD2CH(CH3)2 H
    821.
    Figure US20170324049A1-20171109-C00488
         		H C(CH3)3 H
    822.
    Figure US20170324049A1-20171109-C00489
         		H CD2C(CH3)3 H
    823.
    Figure US20170324049A1-20171109-C00490
         		H CD2CH2CF3 H
    824.
    Figure US20170324049A1-20171109-C00491
         		H CD2C(CH3)2CF3 H
    825.
    Figure US20170324049A1-20171109-C00492
         		H
    Figure US20170324049A1-20171109-C00493
         		H
    826.
    Figure US20170324049A1-20171109-C00494
         		H
    Figure US20170324049A1-20171109-C00495
         		H
    827.
    Figure US20170324049A1-20171109-C00496
         		H
    Figure US20170324049A1-20171109-C00497
         		H
    828.
    Figure US20170324049A1-20171109-C00498
         		H
    Figure US20170324049A1-20171109-C00499
         		H
    829.
    Figure US20170324049A1-20171109-C00500
         		H
    Figure US20170324049A1-20171109-C00501
         		H
    830.
    Figure US20170324049A1-20171109-C00502
         		H
    Figure US20170324049A1-20171109-C00503
         		H
    831.
    Figure US20170324049A1-20171109-C00504
         		H CD2CH3 H
    832.
    Figure US20170324049A1-20171109-C00505
         		H CD(CH3)2 H
    833.
    Figure US20170324049A1-20171109-C00506
         		H CD2CH(CH3)2 H
    834.
    Figure US20170324049A1-20171109-C00507
         		H C(CH3)3 H
    835.
    Figure US20170324049A1-20171109-C00508
         		H CD2C(CH3)3 H
    836.
    Figure US20170324049A1-20171109-C00509
         		H CD2CH2CF3 H
    837.
    Figure US20170324049A1-20171109-C00510
         		H CD2C(CH3)2CF3 H
    838.
    Figure US20170324049A1-20171109-C00511
         		H
    Figure US20170324049A1-20171109-C00512
         		H
    839.
    Figure US20170324049A1-20171109-C00513
         		H
    Figure US20170324049A1-20171109-C00514
         		H
    840.
    Figure US20170324049A1-20171109-C00515
         		H
    Figure US20170324049A1-20171109-C00516
         		H
    841.
    Figure US20170324049A1-20171109-C00517
         		H
    Figure US20170324049A1-20171109-C00518
         		H
    842.
    Figure US20170324049A1-20171109-C00519
         		H
    Figure US20170324049A1-20171109-C00520
         		H
    843.
    Figure US20170324049A1-20171109-C00521
         		H
    Figure US20170324049A1-20171109-C00522
         		H
    844.
    Figure US20170324049A1-20171109-C00523
         		H CD2CH3 H
    845.
    Figure US20170324049A1-20171109-C00524
         		H CD(CH3)2 H
    846.
    Figure US20170324049A1-20171109-C00525
         		H CD2CH(CH3)2 H
    847.
    Figure US20170324049A1-20171109-C00526
         		H C(CH3)3 H
    848.
    Figure US20170324049A1-20171109-C00527
         		H CD2C(CH3)3 H
    849.
    Figure US20170324049A1-20171109-C00528
         		H CD2CH2CF3 H
    850.
    Figure US20170324049A1-20171109-C00529
         		H CD2C(CH3)2CF3 H
    851.
    Figure US20170324049A1-20171109-C00530
         		H
    Figure US20170324049A1-20171109-C00531
         		H
    852.
    Figure US20170324049A1-20171109-C00532
         		H
    Figure US20170324049A1-20171109-C00533
         		H
    853.
    Figure US20170324049A1-20171109-C00534
         		H
    Figure US20170324049A1-20171109-C00535
         		H
    854.
    Figure US20170324049A1-20171109-C00536
         		H
    Figure US20170324049A1-20171109-C00537
         		H
    855.
    Figure US20170324049A1-20171109-C00538
         		H
    Figure US20170324049A1-20171109-C00539
         		H
    856.
    Figure US20170324049A1-20171109-C00540
         		H
    Figure US20170324049A1-20171109-C00541
         		H
  • In one embodiment, the compound is the Compound x having the Formula Ir(LAi)(LBj)2;
  • wherein x=856i+j−856; i is an integer from 1 to 111; and/is an integer from 1 to 856; and
  • wherein LB1 to LB856 have the following structure:
  • Figure US20170324049A1-20171109-C00542
  • wherein LB1 to LB856 are defined according to the above table.
  • In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
  • According to another aspect of the present disclosure, an OLED is also provided. The OLED includes an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may include a host and a phosphorescent dopant. The organic layer can include a compound according to Formula I, and its variations as described herein.
  • The OLED can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer 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.
  • According to another aspect of the present disclosure, a consumer product comprising an OLED is provided. The OLED may include an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer may include a host and one or more emitter dopants. In one embodiment, the organic layer includes a compound of Formula I.
  • Non-limiting examples of consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), wearable device, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays that are less than 2 inches diagonal, 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, and/or signs.
  • The organic layer can also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the hosts used maybe a) bipolar, b) electron transporting, c) hole transporting or d) wide band gap materials that play little role in charge transport. In some embodiments, the host can include a metal complex. 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, and CnH2n—Ar1, or the host has 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 an inorganic compound. For example, a Zn containing inorganic material e.g. ZnS.
  • The host can be a compound comprising at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. The host can include a metal complex. The host can be, but is not limited to, a specific compound selected from the group consisting of:
  • Figure US20170324049A1-20171109-C00543
    Figure US20170324049A1-20171109-C00544
    Figure US20170324049A1-20171109-C00545
    Figure US20170324049A1-20171109-C00546
    Figure US20170324049A1-20171109-C00547
  • and combinations thereof.
  • Additional information on possible hosts is provided below.
  • In yet another aspect of the present disclosure, a formulation that comprises a compound according to Formula I is described. 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.
    • Conductivity Dopants:
  • A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
  • Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804 and US2012146012.
  • Figure US20170324049A1-20171109-C00548
    Figure US20170324049A1-20171109-C00549
    Figure US20170324049A1-20171109-C00550
    • 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 are not limited 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 phosphoric 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 US20170324049A1-20171109-C00551
  • Each of Ar1 to Ar9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, cluysene, perylene, and azulene; the group consisting of 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 the group consisting of 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. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroatyl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
  • In one aspect, Ar1 Ar9 is independently selected from the group consisting of:
  • Figure US20170324049A1-20171109-C00552
  • 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 are not limited to the following general formula:
  • Figure US20170324049A1-20171109-C00553
  • 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.
  • Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, US06517957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.
  • Figure US20170324049A1-20171109-C00554
    Figure US20170324049A1-20171109-C00555
    Figure US20170324049A1-20171109-C00556
    Figure US20170324049A1-20171109-C00557
    Figure US20170324049A1-20171109-C00558
    Figure US20170324049A1-20171109-C00559
    Figure US20170324049A1-20171109-C00560
    Figure US20170324049A1-20171109-C00561
    Figure US20170324049A1-20171109-C00562
    Figure US20170324049A1-20171109-C00563
    Figure US20170324049A1-20171109-C00564
    Figure US20170324049A1-20171109-C00565
    Figure US20170324049A1-20171109-C00566
    Figure US20170324049A1-20171109-C00567
    Figure US20170324049A1-20171109-C00568
    • EBL:
  • An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and or longer lifetime, 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 some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
    • 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. 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 US20170324049A1-20171109-C00569
  • wherein Met is a metal; Y103-Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L101 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 US20170324049A1-20171109-C00570
  • 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 other organic compounds used as host are selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, cluysene, perylene, and azulene; the group consisting of 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 the group consisting of 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. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of 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, the host compound contains at least one of the following groups in the molecule:
  • Figure US20170324049A1-20171109-C00571
    Figure US20170324049A1-20171109-C00572
  • wherein each of 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, heteroatyl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroatyl, 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.
  • Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472,
  • Figure US20170324049A1-20171109-C00573
    Figure US20170324049A1-20171109-C00574
    Figure US20170324049A1-20171109-C00575
    Figure US20170324049A1-20171109-C00576
    Figure US20170324049A1-20171109-C00577
    Figure US20170324049A1-20171109-C00578
    Figure US20170324049A1-20171109-C00579
    Figure US20170324049A1-20171109-C00580
    Figure US20170324049A1-20171109-C00581
    Figure US20170324049A1-20171109-C00582
    Figure US20170324049A1-20171109-C00583
    Figure US20170324049A1-20171109-C00584
    • Additional Emitters:
  • One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
  • Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, US06699599, US06916554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. No. 6,303,238, U.S. Pat. No. 6,413,656, U.S. Pat. No. 6,653,654, U.S. Pat. No. 6,670,645, U.S. Pat. No. 6,687,266, U.S. Pat. No. 6,835,469, U.S. Pat. No. 6,921,915, U.S. Pat. No. 7,279,704, U.S. Pat. No. 7,332,232, U.S. Pat. No. 7,378,162, U.S. Pat. No. 7,534,505, U.S. Pat. No. 7,675,228, U.S. Pat. No. 7,728,137, U.S. Pat. No. 7,740,957, U.S. Pat. No. 7,759,489, U.S. Pat. No. 7,951,947, U.S. Pat. No. 8,067,099, U.S. Pat. No. 8,592,586, U.S. Pat. No. 8,871,361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.
  • Figure US20170324049A1-20171109-C00585
    Figure US20170324049A1-20171109-C00586
    Figure US20170324049A1-20171109-C00587
    Figure US20170324049A1-20171109-C00588
    Figure US20170324049A1-20171109-C00589
    Figure US20170324049A1-20171109-C00590
    Figure US20170324049A1-20171109-C00591
    Figure US20170324049A1-20171109-C00592
    Figure US20170324049A1-20171109-C00593
    Figure US20170324049A1-20171109-C00594
    Figure US20170324049A1-20171109-C00595
    Figure US20170324049A1-20171109-C00596
    Figure US20170324049A1-20171109-C00597
    Figure US20170324049A1-20171109-C00598
    Figure US20170324049A1-20171109-C00599
    Figure US20170324049A1-20171109-C00600
    Figure US20170324049A1-20171109-C00601
    Figure US20170324049A1-20171109-C00602
    Figure US20170324049A1-20171109-C00603
    Figure US20170324049A1-20171109-C00604
    Figure US20170324049A1-20171109-C00605
    Figure US20170324049A1-20171109-C00606
    Figure US20170324049A1-20171109-C00607
    Figure US20170324049A1-20171109-C00608
    • 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 and/or longer lifetime 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 some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and or higher triplet energy than one or more of the hosts closest to the HBL interface.
  • 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 US20170324049A1-20171109-C00609
  • 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 US20170324049A1-20171109-C00610
  • 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 heteroalyl, it has the similar definition as Ar's mentioned above. Ar1 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 US20170324049A1-20171109-C00611
  • 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.
  • Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. No. 6,656,612, U.S. Pat. No. 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,
  • Figure US20170324049A1-20171109-C00612
    Figure US20170324049A1-20171109-C00613
    Figure US20170324049A1-20171109-C00614
    Figure US20170324049A1-20171109-C00615
    Figure US20170324049A1-20171109-C00616
    Figure US20170324049A1-20171109-C00617
    Figure US20170324049A1-20171109-C00618
    Figure US20170324049A1-20171109-C00619
    Figure US20170324049A1-20171109-C00620
    • Charge Generation Layer (CGL)
  • In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
  • 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. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
    • Experimental
    • Synthesis of compound 1
    • Step 1.
  • Figure US20170324049A1-20171109-C00621
  • Sythesis of 3-methyl-N-(2-nitrophenyl)pyrazin-2-amine: 3-methylpyrazin-2-amine (6 g, 55.0 mmol), 1-bromo-2-nitrobenzene (12.77 g, 63.2 mmol), cesium carbonate (35.7 g, 110 mmol), tris(dibenzylideneacetone)palladium(0) (1.509 g, 1.649 mmol) and BiNAP (4.10 g, 6.60 mmol) were charged into the reaction flask with 350 mL of toluene. This mixture was degassed with nitrogen then was heated at reflux for 16 h. GC/MS analysis showed this reaction to be complete. Heating was discontinued. The reaction mixture was filtered and concentrated under vacuum. The crude residue was subjected to column chromatography on silica gel, eluted with a gradient mixture of 2-5% ethyl acetate/toluene, yielding 3-methyl-N-(2-nitrophenyflpyrazin-2-amine (10 g, 43.4 mmol, 79% yield) as a yellow solid.
    • Step 2
  • Figure US20170324049A1-20171109-C00622
  • Synthesis of N1-(3-methylpyrazin-2-yl)benzene-1,2-diamine: 3-methyl-N-(2-nitrophenyl)pyrazin-2-amine (9 g, 39.1 mmol) was dissolved in 200 mL of ethanol. This solution was transferred into a Parr® vessel that contained palladium on carbon (1.5 g, 39.1 mmol) and hydrogenated for 1 hour. The reaction mixture was filtered through a pad of celite. The filtrate was concentrated under vacuum, then triturated with heptane. A tan solid was filtered off and recrystallized from 100 mL of ethanol, yielding 4.35 g of a crystalin solid. The filtrate was concentrated under vacuum to a reduced volume and a 2nd crop of product was isolated via filtration, yielding 2.5 g of pure product.
  • The two product crops were combined yielding N1-(3-methylpyrazin-2-yl)benzene-1,2-diamine (4.35 g, 21.72 mmol, 63.5% yield).
    • Step 3
  • Figure US20170324049A1-20171109-C00623
  • Synthesis of 1-(3-methylpyrazin-2-yl)-2-phenyl-1H-benzo[d]imidazole: N1-(3-methylpyrazin-2-yl)benzene-1,2-diamine (6.85 g, 34.2 mmol), benzaldehyde (4.36 g, 41.0 mmol) and sodium bisulfite (7.12 g, 68.4 mmol) were charged into the reaction flask with 125 mL of DMF. This mixture was stirred and heated at a bath temperature of 125° C. for 16 h under an air atmosphere. TLC of the reaction mixture showed a major product and no unreacted starting material. The reaction mixture was cooled to room temperature, diluted with 300 mL water and then was extracted with 2×350 mL of ethyl acetate. These extracts were combined and were washed with aqueous LiCl. The extracts were dried over magnesium sulfate and filtered and concentrated under vacuum. The crude residue was subjected to column chromatography on silica gel, eluting with a 15-20% ethyl acetate/toluene gradient mixture, providing 1-(3-methylpyrazin-2-yl)-2-phenyl-1H-benzo[d]imidazole (7.0 g, 24.45 mmol, 71.5% yield) as a tan solid.
    • Step 4
  • Figure US20170324049A1-20171109-C00624
  • Synthesis of 1-(3-(lmethyl-d3)pyrazin-2-yl)-2-phenyl-1H-benzo[d]imidazole: 1-(3-methylpyrazin-2-yl)-2-phenyl-1H-benzo[d]imidazole (7.14 g, 24.94 mmol) was dissolved in 70 mL of THF. Dimethyl sulfoxide-d6 (60m1, 857 mmol) was then added to the reaction mixture followed by sodium tert-butoxide (1.197 g, 12.47 mmol). Stirring was continued at room temperature for 18 hours. The dark reaction mixture was quenched with 80 mL D2O and stirred at room temperature for 1 hour. The reaction mixture was diluted with 300 mL water and was extracted with 3×250 mL ethyl acetate. The extracts were combined and washed with aqueous LiCl followed by drying over magnesium sulfate. The extract was filtered and concentrated under vacuum. The crude residue was subjected to column chromatography on silica gel columns, eluted with a 15-20% ethyl acetate/toluene gradient mixture, providing 1-(3-(1methyl-d3)pyrazin-2-yl)-2-phenyl-1H-benzo[d]imidazole (2.95 g, 10.20 mmol, 40.9% yield) as a tan solid.
    • Step 5
  • Figure US20170324049A1-20171109-C00625
  • The iridium salt (4.6 g, 6.44 mmol) and 1-(3-(methyl-d3)pyrazin-2-yl)-2-phenyl-1H-benzo[d]imidazole (2.95 g, 10.20 mmol) were suspended in a 120 mL methanol and ethanol (1/1;v/v) mixture, degassed with nitrogen, and then immersed in an oil bath at 75° C. for 16 h. HPLC showed trace product. The reaction mixture was evaporated under reduced pressure and 60 mL of fresh ethanol was added. This mixture was degassed again and heated in an oil bath set at 90° C. for 24 hours. HPLC still showed very little product formation. The ethanol was removed and was replaced with DMF and 2-ethoxyethanol. The reaction mixture was degassed with nitrogen and was heated in an oil bath at 130° C. for 2 1/2 days. The reaction mixture was then cooled down to room temperature. The solvents were removed under vacuum and the crude residue was subjected to column chromatography on a silica gel column, eluted with DCM followed by DCM/ethyl acetate (1/1;v/v). The solvents were removed and the product residue was purified by column chromatography.
  • The first product eluted from the column was isolated as an orange solid. This material was dissolved in 300 mL DCM and passed through a pad of activated basic alumina The filtrate was evaporated under reduced vacuum. This residue was passed through 7×120g silica gel columns The columns were eluted with 5-10% ethyl acetate/toluene. The pure product fractions were combined and concentrated under vacuum, yielding the iridium complex as an orange solid (0.60g, 0.76 mmol, 11.8% yield)
  • LC/MS analysis confirmed the mass of the desired product.
    • Synthesis of compound 2
    • Step 1
  • Figure US20170324049A1-20171109-C00626
  • In an oven-dried 500 mL two-necked round-bottomed flask 1-bromo-2-nitrobenzene (18.33 g, 91 mmol), 4-methylpyrimidin-5-amine (9 g, 82 mmol), cesium carbonate (53.7 g, 165 mmol), Pd2(dba)3 (1.510 g, 1.649 mmol) and 2,2′-bis(diphenylphosphanyl)-1,1′-binaphthalene (BINAP) (5.14 g, 8.25 mmol) were dissolved in toluene (180 ml) under nitrogen to give a red suspension. The reaction mixture was degassed and heated to 120° C. for 16 h. The mixture was cooled down, diluted with ethyl acetate, washed with brine, filtered through celite and evaporated, providing 4-methyl-N-(2-nitrophenyl)pyrimidin-5-amine as a red solid (10.1 g, 53% yield).
    • Step 2
  • Figure US20170324049A1-20171109-C00627
  • 4-Methyl-N-(2-nitrophenyl)pyrimidin-5-amine (10 g, 43.4 mmol) with 1 g of 10% Pd/C in 200 mL of ethanol was reduced in the Parr hydrogenator at room temperature for 3 h. The reaction mixture was filtered through a celite pad, concentrated, and the precipitated product was filtered off. The product was crystallized from hot DCM to yield a grey solid (7.7 g, 89% yield).
    • Step 3
  • Figure US20170324049A1-20171109-C00628
  • In a nitrogen flushed 500 mL round-bottomed flask, N1-(4-methylpyrimidin-5-yl)benzene-1,2-diamine (7.95 g, 39.7 mmol), benzaldehyde (5.18 g, 48.8 mmol), and Na2S2O5 (15.09 g, 79 mmol) (mixture of sulfite and metabisulfite) were dissolved in DMF (105 ml) open to air to give a yellow solution. The reaction mixture was heated for 16 h at 125° C. open to air. The reaction mixture was then cooled down, diluted with EtOAc, and washed with brine and LiCl aq.10% solution. The organic layer was filtered and evaporated. The product was isolated by column chromatography on silica gel, eluted with DCM/EtOAc 1/1 (v/v), then ciystallyzed from DCM/heptanes, providing brown crystals (7.1 g, 63% yield).
    • Step 4
  • Figure US20170324049A1-20171109-C00629
  • 1-(4-Methylpyrimidin-5-yl)-2-phenyl-1H-benzo [d]imidazole (7.3 g, 25.5 mmol) was dissolved in DMSO-d6 (64.4 g, 765 mmol), and sodium 2-methylpropan-2-olate (1.225 g, 12.75 mmol) was added. The reaction mixture was degassed, immersed in an oil bath, and stirred at 71° C. overnight. The reaction mixture was then cooled down, diluted with brine, and extracted with ethyl acetate (3×50 mL). The extracts were combined, dried over sodium sulfate, filtered and evaporated. The crude mixture was purified by column chromatography on silica gel, eluted with DCM/EtOAc 1/1 (v/v), and recrystallized from DCM/heptanes to afford white crystals (5.1 g, 69% yield).
    • Step 5
  • Figure US20170324049A1-20171109-C00630
  • 1-(4-(methyl-d3)pyrimidin-5-yl)-2-phenyl-1H-benzo[d]imidazole (2.5 g, 8.6 mmol) and iridium triflate complex (6.2 g, 8.6 mmol) were suspended in 50 mL ethoxyethanol/DMF 1/1 (v/v) and heated to 150° C. under nitrogen for 50 h. Then the reaction mixture was cooled down, filtered through a short celite plug, and evaporated. The crude mixture was subjected to column chromatography on a silica gel column eluted with toluene/EtOAc 9/1 (v/v), providing the target compound as yellow solid (1.5 g, 22% yield).
    • Device Examples
  • All example devices were fabricated by high vacuum (<10−7 Torr) thermal evaporation. The anode electrode was 750 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of Liq (8-hydroxyquinoline lithium) followed by 1,000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O2O2) immediately after fabrication with a moisture getter incorporated inside the package. The organic stack of the device examples consisted of sequentially, from the ITO Surface: 100Å of HAT-CN as the hole injection layer (HIL); 450 Å of HTM as a hole transporting layer (HTL); emissive layer (EML) with thickness 400 Å. Emissive layer containing H-host (H1): E-host (H2) in 6:4 ratio and 12 weight % of green emitter. 350 Å of Liq (8-hydroxyquinoline lithium) doped with 40% of ETM as the ETL. Device structure is shown in the table 1. Table 1 shows the schematic device structure. The chemical structures of the device materials are shown below.
  • Figure US20170324049A1-20171109-C00631
    Figure US20170324049A1-20171109-C00632
  • Upon fabrication, the devices were lifetested at DC 80 mA/cm2 and EL and JVL were measured. LT95 at 1,000 nits was calculated from 80 mA/cm2 LT data assuming an acceleration factor of 1.8. Device performance is shown in the table 2
  • TABLE 1
    Device structure
    Layer Material Thickness [Å]
    Anode ITO 800
    HIL HAT-CN 100
    HTL HTM 450
    Green EML H1:H2: example dopant 400
    ETL Liq:ETM 40% 350
    EIL Liq 10
    Cathode Al 1,000
  • TABLE 2
    Device performance
    1931 CIE At 10 mA/cm2
    Emitter λ max FWHM Voltage LE EQE
    15% x y [nm] [nm] [V] [cd/A] [%]
    Compound 1 0.391 0.581 539 87 5.1 67.8 20.0
    Comparative 0.320 0.627 520 70 4.6 66.2 18.5
    Example 1
    Compound 2 0.391 0.582 539 85 5.4 68.6 20.3
  • Comparing compound 1 and 2 with the comparative example 1, the efficiency of compound 1 and 2 is higher than the comparative example. While not wishing to be bound by any particular theory, it is possible that the electon deficiency ring in the peripheral position promotes the electron trapping of the dopant and increases the efficiency. The concept is illustrated in the following picture.
  • Figure US20170324049A1-20171109-C00633
  • 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 (16)

We claim:
1. A compound having the structure of (LA)nIr(LB)3-n represented by Formula I:
Figure US20170324049A1-20171109-C00634
wherein R2, R3, R4 and R5 each represent monosubstitution, disubstitution, trisubstitution, tetrasubstitution, or no substitution;
wherein R1 is an aryl or heteroaryl comprising at least one group selected from group A consisting of:
Figure US20170324049A1-20171109-C00635
Figure US20170324049A1-20171109-C00636
Figure US20170324049A1-20171109-C00637
wherein R1 can be further substituted with one or more substituents selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, and combinations thereof;
wherein R2, R3, R4, and R5 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, and combinations thereof; and
wherein n is 1 or 2.
2. The compound of claim 1, wherein n is 1.
Figure US20170324049A1-20171109-C00638
3. The compound of claim 1, wherein R1 is
wherein R1′ and R2′ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;
wherein at least one of R1′ and R2′ is not hydrogen or deuterium;
wherein A is a 5-membered or 6-membered carbocyclic or heterocyclic aromatic ring that is optionally further substituted; and
wherein at least one of R1′, R2′, and ring A comprise at least one group selected from group A.
4. The compound of claim 1, wherein the compound has the formula:
Figure US20170324049A1-20171109-C00639
wherein R8 represents monosubstitution, disubstitution, trisubstitution, or no substitution;
wherein R6, R7, and R8 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; and
wherein at least one of R6, R7, and R8 comprises at least one group selected from group A.
5. The compound of claim 1, wherein the compound has the formula:
Figure US20170324049A1-20171109-C00640
wherein X1, X2, X3, X4, and X5 are each independently selected from the group consisting of carbon, and nitrogen, and wherein at least one of X1, X2, X3, X4, and X5 is nitrogen; and
wherein R is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, and combinations thereof.
6. The compound of claim 1, wherein LA is selected from the group consisting of:
Figure US20170324049A1-20171109-C00641
Figure US20170324049A1-20171109-C00642
Figure US20170324049A1-20171109-C00643
Figure US20170324049A1-20171109-C00644
Figure US20170324049A1-20171109-C00645
Figure US20170324049A1-20171109-C00646
Figure US20170324049A1-20171109-C00647
Figure US20170324049A1-20171109-C00648
Figure US20170324049A1-20171109-C00649
Figure US20170324049A1-20171109-C00650
Figure US20170324049A1-20171109-C00651
Figure US20170324049A1-20171109-C00652
Figure US20170324049A1-20171109-C00653
Figure US20170324049A1-20171109-C00654
Figure US20170324049A1-20171109-C00655
Figure US20170324049A1-20171109-C00656
Figure US20170324049A1-20171109-C00657
Figure US20170324049A1-20171109-C00658
Figure US20170324049A1-20171109-C00659
Figure US20170324049A1-20171109-C00660
Figure US20170324049A1-20171109-C00661
Figure US20170324049A1-20171109-C00662
7. The compound of claim 1, wherein LB is selected from the group consisting of:
LB
Figure US20170324049A1-20171109-C00663
 LB RB1 RB2 RB3 RB4 1. H H H H 2. CH3 H H H 3. H CH3 H H 4. H H CH3 H 5. H H H CH3 6. CH3 H CH3 H 7. CH3 H H CH3 8. H CH3 CH3 H 9. H CH3 H CH3 10. H H CH3 CH3 11. CH3 CH3 CH3 H 12. CH3 CH3 H CH3 13. CH3 H CH3 CH3 14. H CH3 CH3 CH3 15. CH3 CH3 CH3 CH3 16. CH2CH3 H H H 17. CH2CH3 CH3 H CH3 18. CH2CH3 H CH3 H 19. CH2CH3 H H CH3 20. CH2CH3 CH3 CH3 H 21. CH2CH3 CH3 H CH3 22. CH2CH3 H CH3 CH3 23. CH2CH3 CH3 CH3 CH3 24. H CH2CH3 H H 25. CH3 CH2CH3 H CH3 26. H CH2CH3 CH3 H 27. H CH2CH3 H CH3 28. CH3 CH2CH3 CH3 H 29. CH3 CH2CH3 H CH3 30. H CH2CH3 CH3 CH3 31. CH3 CH2CH3 CH3 CH3 32. H H CH2CH3 H 33. CH3 H CH2CH3 H 34. H CH3 CH2CH3 H 35. H H CH2CH3 CH3 36. CH3 CH3 CH2CH3 H 37. CH3 H CH2CH3 CH3 38. H CH3 CH2CH3 CH3 39. CH3 CH3 CH2CH3 CH3 40. CH(CH3)2 H H H 41. CH(CH3)2 CH3 H CH3 42. CH(CH3)2 H CH3 H 43. CH(CH3)2 H H CH3 44. CH(CH3)2 CH3 CH3 H 45. CH(CH3)2 CH3 H CH3 46. CH(CH3)2 H CH3 CH3 47. CH(CH3)2 CH3 CH3 CH3 48. H CH(CH3)2 H H 49. CH3 CH(CH3)2 H CH3 50. H CH(CH3)2 CH3 H 51. H CH(CH3)2 H CH3 52. CH3 CH(CH3)2 CH3 H 53. CH3 CH(CH3)2 H CH3 54. H CH(CH3)2 CH3 CH3 55. CH3 CH(CH3)2 CH3 CH3 56. H H CH(CH3)2 H 57. CH3 H CH(CH3)2 H 58. H CH3 CH(CH3)2 H 59. H H CH(CH3)2 CH3 60. CH3 CH3 CH(CH3)2 H 61. CH3 H CH(CH3)2 CH3 62. H CH3 CH(CH3)2 CH3 63. CH3 CH3 CH(CH3)2 CH3 64. CH2CH(CH3)2 H H H 65. CH2CH(CH3)2 CH3 H CH3 66. CH2CH(CH3)2 H CH3 H 67. CH2CH(CH3)2 H H CH3 68. CH2CH(CH3)2 CH3 CH3 H 69. CH2CH(CH3)2 CH3 H CH3 70. CH2CH(CH3)2 H CH3 CH3 71. CH2CH(CH3)2 CH3 CH3 CH3 72. H CH2CH(CH3)2 H H 73. CH3 CH2CH(CH3)2 H CH3 74. H CH2CH(CH3)2 CH3 H 75. H CH2CH(CH3)2 H CH3 76. CH3 CH2CH(CH3)2 CH3 H 77. CH3 CH2CH(CH3)2 H CH3 78. H CH2CH(CH3)2 CH3 CH3 79. CH3 CH2CH(CH3)2 CH3 CH3 80. H H CH2CH(CH3)2 H 81. CH3 H CH2CH(CH3)2 H 82. H CH3 CH2CH(CH3)2 H 83. H H CH2CH(CH3)2 CH3 84. CH3 CH3 CH2CH(CH3)2 H 85. CH3 H CH2CH(CH3)2 CH3 86. H CH3 CH2CH(CH3)2 CH3 87. CH3 CH3 CH2CH(CH3)2 CH3 88. C(CH3)3 H H H 89. C(CH3)3 CH3 H CH3 90. C(CH3)3 H CH3 H 91. C(CH3)3 H H CH3 92. C(CH3)3 CH3 CH3 H 93. C(CH3)3 CH3 H CH3 94. C(CH3)3 H CH3 CH3 95. C(CH3)3 CH3 CH3 CH3 96. H C(CH3)3 H H 97. CH3 C(CH3)3 H CH3 98. H C(CH3)3 CH3 H 99. H C(CH3)3 H CH3 100. CH3 C(CH3)3 CH3 H 101. CH3 C(CH3)3 H CH3 102. H C(CH3)3 CH3 CH3 103. CH3 C(CH3)3 CH3 CH3 104. H H C(CH3)3 H 105. CH3 H C(CH3)3 H 106. H CH3 C(CH3)3 H 107. H H C(CH3)3 CH3 108. CH3 CH3 C(CH3)3 H 109. CH3 H C(CH3)3 CH3 110. H CH3 C(CH3)3 CH3 111. CH3 CH3 C(CH3)3 CH3 112. CH2C(CH3)3 H H H 113. CH2C(CH3)3 CH3 H CH3 114. CH2C(CH3)3 H CH3 H 115. CH2C(CH3)3 H H CH3 116. CH2C(CH3)3 CH3 CH3 H 117. CH2C(CH3)3 CH3 H CH3 118. CH2C(CH3)3 H CH3 CH3 119. CH2C(CH3)3 CH3 CH3 CH3 120. H CH2C(CH3)3 H H 121. CH3 CH2C(CH3)3 H CH3 122. H CH2C(CH3)3 CH3 H 123. H CH2C(CH3)3 H CH3 124. CH3 CH2C(CH3)3 CH3 H 125. CH3 CH2C(CH3)3 H CH3 126. H CH2C(CH3)3 CH3 CH3 127. CH3 CH2C(CH3)3 CH3 CH3 128. H H CH2C(CH3)3 H 129. CH3 H CH2C(CH3)3 H 130. H CH3 CH2C(CH3)3 H 131. H H CH2C(CH3)3 CH3 132. CH3 CH3 CH2C(CH3)3 H 133. CH3 H CH2C(CH3)3 CH3 134. H CH3 CH2C(CH3)3 CH3 135. CH3 CH3 CH2C(CH3)3 CH3 136. CH2C(CH3)2CF3 H H H 137. CH2C(CH3)2CF3 CH3 H CH3 138. CH2C(CH3)2CF3 H CH3 H 139. CH2C(CH3)2CF3 H H CH3 140. CH2C(CH3)2CF3 CH3 CH3 H 141. CH2C(CH3)2CF3 CH3 H CH3 142. CH2C(CH3)2CF3 H CH3 CH3 143. CH2C(CH3)2CF3 CH3 CH3 CH3 144. H CH2C(CH3)2CF3 H H 145. CH3 CH2C(CH3)2CF3 H CH3 146. H CH2C(CH3)2CF3 CH3 H 147. H CH2C(CH3)2CF3 H CH3 148. CH3 CH2C(CH3)2CF3 CH3 H 149. CH3 CH2C(CH3)2CF3 H CH3 150. H CH2C(CH3)2CF3 CH3 CH3 151. CH3 CH2C(CH3)2CF3 CH3 CH3 152. H H CH2C(CH3)2CF3 H 153. CH3 H CH2C(CH3)2CF3 H 154. H CH3 CH2C(CH3)2CF3 H 155. H H CH2C(CH3)2CF3 CH3 156. CH3 CH3 CH2C(CH3)2CF3 H 157. CH3 H CH2C(CH3)2CF3 CH3 158. H CH3 CH2C(CH3)2CF3 CH3 159. CH3 CH3 CH2C(CH3)2CF3 CH3 160. CH2CH2CF3 H H H 161. CH2CH2CF3 CH3 H CH3 162. CH2CH2CF3 H CH3 H 163. CH2CH2CF3 H H CH3 164. CH2CH2CF3 CH3 CH3 H 165. CH2CH2CF3 CH3 H CH3 166. CH2CH2CF3 H CH3 CH3 167. CH2CH2CF3 CH3 CH3 CH3 168. H CH2CH2CF3 H H 169. CH3 CH2CH2CF3 H CH3 170. H CH2CH2CF3 CH3 H 171. H CH2CH2CF3 H CH3 172. CH3 CH2CH2CF3 CH3 H 173. CH3 CH2CH2CF3 H CH3 174. H CH2CH2CF3 CH3 CH3 175. CH3 CH2CH2CF3 CH3 CH3 176. H H CH2CH2CF3 H 177. CH3 H CH2CH2CF3 H 178. H CH3 CH2CH2CF3 H 179. H H CH2CH2CF3 CH3 180. CH3 CH3 CH2CH2CF3 H 181. CH3 H CH2CH2CF3 CH3 182. H CH3 CH2CH2CF3 CH3 183. CH3 CH3 CH2CH2CF3 CH3 184.
Figure US20170324049A1-20171109-C00664
 H H H 185.
Figure US20170324049A1-20171109-C00665
 CH3 H CH3 186.
Figure US20170324049A1-20171109-C00666
 H CH3 H 187.
Figure US20170324049A1-20171109-C00667
 H H CH3 188.
Figure US20170324049A1-20171109-C00668
 CH3 CH3 H 189.
Figure US20170324049A1-20171109-C00669
 CH3 H CH3 190.
Figure US20170324049A1-20171109-C00670
 H CH3 CH3 191.
Figure US20170324049A1-20171109-C00671
 CH3 CH3 CH3 192. H
Figure US20170324049A1-20171109-C00672
 H H 193. CH3
Figure US20170324049A1-20171109-C00673
 H CH3 194. H
Figure US20170324049A1-20171109-C00674
 CH3 H 195. H
Figure US20170324049A1-20171109-C00675
 H CH3 196. CH3
Figure US20170324049A1-20171109-C00676
 CH3 H 197. CH3
Figure US20170324049A1-20171109-C00677
 H CH3 198. H
Figure US20170324049A1-20171109-C00678
 CH3 CH3 199. CH3
Figure US20170324049A1-20171109-C00679
 CH3 CH3 200. H H
Figure US20170324049A1-20171109-C00680
 H 201. CH3 H
Figure US20170324049A1-20171109-C00681
 H 202. H CH3
Figure US20170324049A1-20171109-C00682
 H 203. H H
Figure US20170324049A1-20171109-C00683
 CH3 204. CH3 CH3
Figure US20170324049A1-20171109-C00684
 H 205. CH3 H
Figure US20170324049A1-20171109-C00685
 CH3 206. H CH3
Figure US20170324049A1-20171109-C00686
 CH3 207. CH3 CH3
Figure US20170324049A1-20171109-C00687
 CH3 208.
Figure US20170324049A1-20171109-C00688
 H H H 209.
Figure US20170324049A1-20171109-C00689
 CH3 H CH3 210.
Figure US20170324049A1-20171109-C00690
 H CH3 H 211.
Figure US20170324049A1-20171109-C00691
 H H CH3 212.
Figure US20170324049A1-20171109-C00692
 CH3 CH3 H 213.
Figure US20170324049A1-20171109-C00693
 CH3 H CH3 214.
Figure US20170324049A1-20171109-C00694
 H CH3 CH3 215.
Figure US20170324049A1-20171109-C00695
 CH3 CH3 CH3 216. H
Figure US20170324049A1-20171109-C00696
 H H 217. CH3
Figure US20170324049A1-20171109-C00697
 H CH3 218. H
Figure US20170324049A1-20171109-C00698
 CH3 H 219. H
Figure US20170324049A1-20171109-C00699
 H CH3 220. CH3
Figure US20170324049A1-20171109-C00700
 CH3 H 221. CH3
Figure US20170324049A1-20171109-C00701
 H CH3 222. H
Figure US20170324049A1-20171109-C00702
 CH3 CH3 223. CH3
Figure US20170324049A1-20171109-C00703
 CH3 CH3 224. H H
Figure US20170324049A1-20171109-C00704
 H 225. CH3 H
Figure US20170324049A1-20171109-C00705
 H 226. H CH3
Figure US20170324049A1-20171109-C00706
 H 227. H H
Figure US20170324049A1-20171109-C00707
 CH3 228. CH3 CH3
Figure US20170324049A1-20171109-C00708
 H 229. CH3 H
Figure US20170324049A1-20171109-C00709
 CH3 230. H CH3
Figure US20170324049A1-20171109-C00710
 CH3 231. CH3 CH3
Figure US20170324049A1-20171109-C00711
 CH3 232.
Figure US20170324049A1-20171109-C00712
 H H H 233.
Figure US20170324049A1-20171109-C00713
 CH3 H CH3 234.
Figure US20170324049A1-20171109-C00714
 H CH3 H 235.
Figure US20170324049A1-20171109-C00715
 H H CH3 236.
Figure US20170324049A1-20171109-C00716
 CH3 CH3 H 237.
Figure US20170324049A1-20171109-C00717
 CH3 H CH3 238.
Figure US20170324049A1-20171109-C00718
 H CH3 CH3 239.
Figure US20170324049A1-20171109-C00719
 CH3 CH3 CH3 240. H
Figure US20170324049A1-20171109-C00720
 H H 241. CH3
Figure US20170324049A1-20171109-C00721
 H CH3 242. H
Figure US20170324049A1-20171109-C00722
 CH3 H 243. H
Figure US20170324049A1-20171109-C00723
 H CH3 244. CH3
Figure US20170324049A1-20171109-C00724
 CH3 H 245. CH3
Figure US20170324049A1-20171109-C00725
 H CH3 246. H
Figure US20170324049A1-20171109-C00726
 CH3 CH3 247. CH3
Figure US20170324049A1-20171109-C00727
 CH3 CH3 248. H H
Figure US20170324049A1-20171109-C00728
 H 249. CH3 H
Figure US20170324049A1-20171109-C00729
 H 250. H CH3
Figure US20170324049A1-20171109-C00730
 H 251. H H
Figure US20170324049A1-20171109-C00731
 CH3 252. CH3 CH3
Figure US20170324049A1-20171109-C00732
 H 253. CH3 H
Figure US20170324049A1-20171109-C00733
 CH3 254. H CH3
Figure US20170324049A1-20171109-C00734
 CH3 255. CH3 CH3
Figure US20170324049A1-20171109-C00735
 CH3 256.
Figure US20170324049A1-20171109-C00736
 H H H 257.
Figure US20170324049A1-20171109-C00737
 CH3 H CH3 258.
Figure US20170324049A1-20171109-C00738
 H CH3 H 259.
Figure US20170324049A1-20171109-C00739
 H H CH3 260.
Figure US20170324049A1-20171109-C00740
 CH3 CH3 H 261.
Figure US20170324049A1-20171109-C00741
 CH3 H CH3 262.
Figure US20170324049A1-20171109-C00742
 H CH3 CH3 263.
Figure US20170324049A1-20171109-C00743
 CH3 CH3 CH3 264. H
Figure US20170324049A1-20171109-C00744
 H H 265. CH3
Figure US20170324049A1-20171109-C00745
 H CH3 266. H
Figure US20170324049A1-20171109-C00746
 CH3 H 267. H
Figure US20170324049A1-20171109-C00747
 H CH3 268. CH3
Figure US20170324049A1-20171109-C00748
 CH3 H 269. CH3
Figure US20170324049A1-20171109-C00749
 H CH3 270. H
Figure US20170324049A1-20171109-C00750
 CH3 CH3 271. CH3
Figure US20170324049A1-20171109-C00751
 CH3 CH3 272. H H
Figure US20170324049A1-20171109-C00752
 H 273. CH3 H
Figure US20170324049A1-20171109-C00753
 H 274. H CH3
Figure US20170324049A1-20171109-C00754
 H 275. H H
Figure US20170324049A1-20171109-C00755
 CH3 276. CH3 CH3
Figure US20170324049A1-20171109-C00756
 H 277. CH3 H
Figure US20170324049A1-20171109-C00757
 CH3 278. H CH3
Figure US20170324049A1-20171109-C00758
 CH3 279. CH3 CH3
Figure US20170324049A1-20171109-C00759
 CH3 280.
Figure US20170324049A1-20171109-C00760
 H H H 281.
Figure US20170324049A1-20171109-C00761
 CH3 H CH3 282.
Figure US20170324049A1-20171109-C00762
 H CH3 H 283.
Figure US20170324049A1-20171109-C00763
 H H CH3 284.
Figure US20170324049A1-20171109-C00764
 CH3 CH3 H 285.
Figure US20170324049A1-20171109-C00765
 CH3 H CH3 286.
Figure US20170324049A1-20171109-C00766
 CH3 CH3 287.
Figure US20170324049A1-20171109-C00767
 CH3 CH3 CH3 288. H
Figure US20170324049A1-20171109-C00768
 H H 289. CH3
Figure US20170324049A1-20171109-C00769
 H CH3 290. H
Figure US20170324049A1-20171109-C00770
 CH3 H 291. H
Figure US20170324049A1-20171109-C00771
 CH3 H 292. CH3
Figure US20170324049A1-20171109-C00772
 CH3 H 293. CH3
Figure US20170324049A1-20171109-C00773
 H CH3 294. H
Figure US20170324049A1-20171109-C00774
 CH3 CH3 295. CH3
Figure US20170324049A1-20171109-C00775
 CH3 CH3 296. H H
Figure US20170324049A1-20171109-C00776
 H 297. CH3 H
Figure US20170324049A1-20171109-C00777
 H 298. H CH3
Figure US20170324049A1-20171109-C00778
 H 299. H H
Figure US20170324049A1-20171109-C00779
 CH3 300. CH3 CH3
Figure US20170324049A1-20171109-C00780
 H 301. CH3 H
Figure US20170324049A1-20171109-C00781
 CH3 302. H CH3
Figure US20170324049A1-20171109-C00782
 CH3 303. CH3 CH3
Figure US20170324049A1-20171109-C00783
 CH3 304.
Figure US20170324049A1-20171109-C00784
 H H H 305.
Figure US20170324049A1-20171109-C00785
 CH3 H CH3 306.
Figure US20170324049A1-20171109-C00786
 H CH3 H 307.
Figure US20170324049A1-20171109-C00787
 H H CH3 308.
Figure US20170324049A1-20171109-C00788
 CH3 CH3 H 309.
Figure US20170324049A1-20171109-C00789
 CH3 H CH3 310.
Figure US20170324049A1-20171109-C00790
 H CH3 CH3 311.
Figure US20170324049A1-20171109-C00791
 CH3 CH3 CH3 312. H
Figure US20170324049A1-20171109-C00792
 H H 313. CH3
Figure US20170324049A1-20171109-C00793
 H CH3 314. H
Figure US20170324049A1-20171109-C00794
 CH3 H 315. H
Figure US20170324049A1-20171109-C00795
 H CH3 316. CH3
Figure US20170324049A1-20171109-C00796
 CH3 H 317. CH3
Figure US20170324049A1-20171109-C00797
 H CH3 318. H
Figure US20170324049A1-20171109-C00798
 CH3 CH3 319. CH3
Figure US20170324049A1-20171109-C00799
 CH3 CH3 320. H H
Figure US20170324049A1-20171109-C00800
 H 321. CH3 H
Figure US20170324049A1-20171109-C00801
 H 322. H CH3
Figure US20170324049A1-20171109-C00802
 H 323. H H
Figure US20170324049A1-20171109-C00803
 CH3 324. CH3 CH3
Figure US20170324049A1-20171109-C00804
 H 325. CH3 H
Figure US20170324049A1-20171109-C00805
 CH3 326. H CH3
Figure US20170324049A1-20171109-C00806
 CH3 327. CH3 CH3
Figure US20170324049A1-20171109-C00807
 CH3 328. CH(CH3)2 H CH2CH3 H 329. CH(CH3)2 H CH(CH3)2 H 330. CH(CH3)2 H CH2CH(CH3)2 H 331. CH(CH3)2 H C(CH3)3 H 332. CH(CH3)2 H CH2C(CH3)3 H 333. CH(CH3)2 H CH2CH2CF3 H 334. CH(CH3)2 H CH2C(CH3)2CF3 H 335. CH(CH3)2 H
Figure US20170324049A1-20171109-C00808
 H 336. CH(CH3)2 H
Figure US20170324049A1-20171109-C00809
 H 337. CH(CH3)2 H
Figure US20170324049A1-20171109-C00810
 H 338. CH(CH3)2 H
Figure US20170324049A1-20171109-C00811
 H 339. CH(CH3)2 H
Figure US20170324049A1-20171109-C00812
 H 340. CH(CH3)2 H
Figure US20170324049A1-20171109-C00813
 H 341. C(CH3)3 H CH2CH3 H 342. C(CH3)3 H CH(CH3)2 H 343. C(CH3)3 H CH2CH(CH3)2 H 344. C(CH3)3 H C(CH3)3 H 345. C(CH3)3 H CH2C(CH3)3 H 346. C(CH3)3 H CH2CH2CF3 H 347. C(CH3)3 H CH2C(CH3)2CF3 H 348. C(CH3)3 H
Figure US20170324049A1-20171109-C00814
 H 349. C(CH3)3 H
Figure US20170324049A1-20171109-C00815
 H 350. C(CH3)3 H
Figure US20170324049A1-20171109-C00816
 H 351. C(CH3)3 H
Figure US20170324049A1-20171109-C00817
 H 352. C(CH3)3 H
Figure US20170324049A1-20171109-C00818
 H 353. C(CH3)3 H
Figure US20170324049A1-20171109-C00819
 H 354. CH2C(CH3)3 H CH2CH3 H 355. CH2C(CH3)3 H CH(CH3)2 H 356. CH2C(CH3)3 H CH2CH(CH3)2 H 357. CH2C(CH3)3 H C(CH3)3 H 358. CH2C(CH3)3 H CH2C(CH3)3 H 359. CH2C(CH3)3 H CH2CH2CF3 H 360. CH2C(CH3)3 H CH2C(CH3)2CF3 H 361. CH2C(CH3)3 H
Figure US20170324049A1-20171109-C00820
 H 362. CH2C(CH3)3 H
Figure US20170324049A1-20171109-C00821
 H 363. CH2C(CH3)3 H
Figure US20170324049A1-20171109-C00822
 H 364. CH2C(CH3)3 H
Figure US20170324049A1-20171109-C00823
 H 365. CH2C(CH3)3 H
Figure US20170324049A1-20171109-C00824
 H 366. CH2C(CH3)3 H
Figure US20170324049A1-20171109-C00825
 H 367.
Figure US20170324049A1-20171109-C00826
 H CH2CH3 H 368.
Figure US20170324049A1-20171109-C00827
 H CH(CH3)2 H 369.
Figure US20170324049A1-20171109-C00828
 H CH2CH(CH3)2 H 370.
Figure US20170324049A1-20171109-C00829
 H C(CH3)3 H 371.
Figure US20170324049A1-20171109-C00830
 H CH2C(CH3)3 H 372.
Figure US20170324049A1-20171109-C00831
 H CH2CH2CF3 H 373.
Figure US20170324049A1-20171109-C00832
 H CH2C(CH3)2CF3 H 374.
Figure US20170324049A1-20171109-C00833
 H
Figure US20170324049A1-20171109-C00834
 H 375.
Figure US20170324049A1-20171109-C00835
 H
Figure US20170324049A1-20171109-C00836
 H 376.
Figure US20170324049A1-20171109-C00837
 H
Figure US20170324049A1-20171109-C00838
 H 377.
Figure US20170324049A1-20171109-C00839
 H
Figure US20170324049A1-20171109-C00840
 H 378.
Figure US20170324049A1-20171109-C00841
 H
Figure US20170324049A1-20171109-C00842
 H 379.
Figure US20170324049A1-20171109-C00843
 H
Figure US20170324049A1-20171109-C00844
 H 380.
Figure US20170324049A1-20171109-C00845
 H CH2CH3 H 381.
Figure US20170324049A1-20171109-C00846
 H CH(CH3)2 H 382.
Figure US20170324049A1-20171109-C00847
 H CH2CH(CH3)2 H 383.
Figure US20170324049A1-20171109-C00848
 H C(CH3)3 H 384.
Figure US20170324049A1-20171109-C00849
 H CH2C(CH3)3 H 385.
Figure US20170324049A1-20171109-C00850
 H CH2CH2CF3 H 386.
Figure US20170324049A1-20171109-C00851
 H CH2C(CH3)2CF3 H 387.
Figure US20170324049A1-20171109-C00852
 H
Figure US20170324049A1-20171109-C00853
 H 388.
Figure US20170324049A1-20171109-C00854
 H
Figure US20170324049A1-20171109-C00855
 H 389.
Figure US20170324049A1-20171109-C00856
 H
Figure US20170324049A1-20171109-C00857
 H 390.
Figure US20170324049A1-20171109-C00858
 H
Figure US20170324049A1-20171109-C00859
 H 391.
Figure US20170324049A1-20171109-C00860
 H
Figure US20170324049A1-20171109-C00861
 H 392.
Figure US20170324049A1-20171109-C00862
 H
Figure US20170324049A1-20171109-C00863
 H 393.
Figure US20170324049A1-20171109-C00864
 H CH2CH(CH3)2 H 394.
Figure US20170324049A1-20171109-C00865
 H C(CH3)3 H 395.
Figure US20170324049A1-20171109-C00866
 H CH2C(CH3)3 H 396.
Figure US20170324049A1-20171109-C00867
 H CH2CH2CF3 H 397.
Figure US20170324049A1-20171109-C00868
 H CH2C(CH3)2CF3 H 398.
Figure US20170324049A1-20171109-C00869
 H
Figure US20170324049A1-20171109-C00870
 H 399.
Figure US20170324049A1-20171109-C00871
 H
Figure US20170324049A1-20171109-C00872
 H 400.
Figure US20170324049A1-20171109-C00873
 H
Figure US20170324049A1-20171109-C00874
 H 401.
Figure US20170324049A1-20171109-C00875
 H
Figure US20170324049A1-20171109-C00876
 H 402.
Figure US20170324049A1-20171109-C00877
 H
Figure US20170324049A1-20171109-C00878
 H 403.
Figure US20170324049A1-20171109-C00879
 H
Figure US20170324049A1-20171109-C00880
 H 404.
Figure US20170324049A1-20171109-C00881
 H CH2CH(CH3)2 H 405.
Figure US20170324049A1-20171109-C00882
 H C(CH3)3 H 406.
Figure US20170324049A1-20171109-C00883
 H CH2C(CH3)3 H 407.
Figure US20170324049A1-20171109-C00884
 H CH2CH2CF3 H 408.
Figure US20170324049A1-20171109-C00885
 H CH2C(CH3)2CF3 H 409.
Figure US20170324049A1-20171109-C00886
 H
Figure US20170324049A1-20171109-C00887
 H 410.
Figure US20170324049A1-20171109-C00888
 H
Figure US20170324049A1-20171109-C00889
 H 411.
Figure US20170324049A1-20171109-C00890
 H
Figure US20170324049A1-20171109-C00891
 H 412.
Figure US20170324049A1-20171109-C00892
 H
Figure US20170324049A1-20171109-C00893
 H 413.
Figure US20170324049A1-20171109-C00894
 H
Figure US20170324049A1-20171109-C00895
 H 414.
Figure US20170324049A1-20171109-C00896
 H
Figure US20170324049A1-20171109-C00897
 H 415.
Figure US20170324049A1-20171109-C00898
 H CH2CH(CH3)2 H 416.
Figure US20170324049A1-20171109-C00899
 H C(CH3)3 H 417.
Figure US20170324049A1-20171109-C00900
 H CH2C(CH3)3 H 418.
Figure US20170324049A1-20171109-C00901
 H CH2CH2CF3 H 419.
Figure US20170324049A1-20171109-C00902
 H CH2C(CH3)2CF3 H 420.
Figure US20170324049A1-20171109-C00903
 H
Figure US20170324049A1-20171109-C00904
 H 421.
Figure US20170324049A1-20171109-C00905
 H
Figure US20170324049A1-20171109-C00906
 H 422.
Figure US20170324049A1-20171109-C00907
 H
Figure US20170324049A1-20171109-C00908
 H 423.
Figure US20170324049A1-20171109-C00909
 H
Figure US20170324049A1-20171109-C00910
 H 424.
Figure US20170324049A1-20171109-C00911
 H
Figure US20170324049A1-20171109-C00912
 H 425.
Figure US20170324049A1-20171109-C00913
 H
Figure US20170324049A1-20171109-C00914
 H 426. H H H H 427. CD3 H H H 428. H CD3 H H 429. H H CD3 H 430. H H H CD3 431. CD3 H CD3 H 432. CD3 H H CD3 433. H CD3 CH3 H 434. H CD3 H CD3 435. H H CD3 CD3 436. CD3 CD3 CD3 H 437. CD3 CD3 H CD3 438. CD3 H CD3 CD3 439. H CD3 CD3 CD3 440. CD3 CD3 CD3 CD3 441. CD2CH3 H H H 442. CD2CH3 CD3 H CD3 443. CD2CH3 H CD3 H 444. CD2CH3 H H CD3 445. CD2CH3 CD3 CD3 H 446. CD2CH3 CD3 H CD3 447. CD2CH3 H CD3 CD3 448. CD2CH3 CD3 CD3 CD3 449. H CD2CH3 H H 450. CH3 CD2CH3 H CD3 451. H CD2CH3 CD3 H 452. H CD2CH3 H CD3 453. CD3 CD2CH3 CD3 H 454. CD3 CD2CH3 H CD3 455. H CD2CH3 CD3 CD3 456. CD3 CD2CH3 CD3 CD3 457. H H CD2CH3 H 458. CD3 H CD2CH3 H 459. H CD3 CD2CH3 H 460. H H CD2CH3 CD3 461. CD3 CD3 CD2CH3 H 462. CD3 H CD2CH3 CD3 463. H CD3 CD2CH3 CD3 464. CD3 CD3 CD2CH3 CD3 465. CD(CH3)2 H H H 466. CD(CH3)2 CD3 H CD3 467. CD(CH3)2 H CD3 H 468. CD(CH3)2 H H CD3 469. CD(CH3)2 CD3 CD3 H 470. CD(CH3)2 CD3 H CD3 471. CD(CH3)2 H CD3 CD3 472. CD(CH3)2 CD3 CD3 CD3 473. H CD(CH3)2 H H 474. CD3 CD(CH3)2 H CD3 475. H CD(CH3)2 CD3 H 476. H CD(CH3)2 H CD3 477. CD3 CD(CH3)2 CD3 H 478. CD3 CD(CH3)2 H CD3 479. H CD(CH3)2 CD3 CD3 480. CD3 CD(CH3)2 CD3 CD3 481. H H CD(CH3)2 H 482. CD3 H CD(CH3)2 H 483. H CD3 CD(CH3)2 H 484. H H CD(CH3)2 CD3 485. CD3 CD3 CD(CH3)2 H 486. CD3 H CD(CH3)2 CD3 487. H CD3 CD(CH3)2 CD3 488. CD3 CD3 CD(CH3)2 CD3 489. CD(CD3)2 H H H 490. CD(CD3)2 CD3 H CD3 491. CD(CD3)2 H CD3 H 492. CD(CD3)2 H H CD3 493. CD(CD3)2 CD3 CD3 H 494. CD(CD3)2 CD3 H CD3 495. CD(CD3)2 H CD3 CD3 496. CD(CD3)2 CD3 CD3 CD3 497. H CD(CD3)2 H H 498. CH3 CD(CD3)2 H CD3 499. H CD(CD3)2 CD3 H 500. H CD(CD3)2 H CD3 501. CD3 CD(CD3)2 CD3 H 502. CD3 CD(CD3)2 H CD3 503. H CD(CD3)2 CD3 CD3 504. CD3 CD(CD3)2 CD3 CD3 505. H H CD(CD3)2 H 506. CD3 H CD(CD3)2 H 507. H CD3 CD(CD3)2 H 508. H H CD(CD3)2 CD3 509. CD3 CD3 CD(CD3)2 H 510. CD3 H CD(CD3)2 CD3 511. H CD3 CD(CD3)2 CD3 512. CD3 CD3 CD(CD3)2 CD3 513. CD2CH(CH3)2 H H H 514. CD2CH(CH3)2 CD3 H CD3 515. CD2CH(CH3)2 H CD3 H 516. CD2CH(CH3)2 H H CD3 517. CD2CH(CH3)2 CD3 CD3 H 518. CD2CH(CH3)2 CD3 H CD3 519. CD2CH(CH3)2 H CD3 CD3 520. CD2CH(CH3)2 CD3 CD3 CD3 521. H CD2CH(CH3)2 H H 522. CD3 CD2CH(CH3)2 H CD3 523. H CD2CH(CH3)2 CD3 H 524. H CD2CH(CH3)2 H CD3 525. CD3 CD2CH(CH3)2 CD3 H 526. CD3 CD2CH(CH3)2 H CD3 527. H CD2CH(CH3)2 CD3 CD3 528. CD3 CD2CH(CH3)2 CD3 CD3 529. H H CD2CH(CH3)2 H 530. CD3 H CD2CH(CH3)2 H 531. H CD3 CD2CH(CH3)2 H 532. H H CD2CH(CH3)2 CD3 533. CD3 CD3 CD2CH(CH3)2 H 534. CD3 H CD2CH(CH3)2 CD3 535. H CD3 CD2CH(CH3)2 CD3 536. CD3 CD3 CD2CH(CH3)2 CD3 537. CD2C(CH3)3 H H H 538. CD2C(CH3)3 CD3 H CD3 539. CD2C(CH3)3 H CD3 H 540. CD2C(CH3)3 H H CD3 541. CD2C(CH3)3 CD3 CD3 H 542. CD2C(CH3)3 CD3 H CD3 543. CD2C(CH3)3 H CD3 CD3 544. CD2C(CH3)3 CH3 CD3 CD3 545. H CD2C(CH3)3 H H 546. CD3 CD2C(CH3)3 H CD3 547. H CD2C(CH3)3 CD3 H 548. H CD2C(CH3)3 H CD3 549. CD3 CD2C(CH3)3 CD3 H 550. CD3 CD2C(CH3)3 H CD3 551. H CD2C(CH3)3 CD3 CD3 552. CD3 CD2C(CH3)3 CD3 CD3 553. H H CD2C(CH3)3 H 554. CD3 H CD2C(CH3)3 H 555. H CD3 CD2C(CH3)3 H 556. H H CD2C(CH3)3 CD3 557. CD3 CD3 CD2C(CH3)3 H 558. CD3 H CD2C(CH3)3 CD3 559. H CD3 CD2C(CH3)3 CD3 560. CD3 CD3 CD2C(CH3)3 CD3 561. CD2C(CH3)2CF3 H H H 562. CD2C(CH3)2CF3 CD3 H CD3 563. CD2C(CH3)2CF3 H CD3 H 564. CD2C(CH3)2CF3 H H CD3 565. CD2C(CH3)2CF3 CD3 CD3 H 566. CD2C(CH3)2CF3 CD3 H CD3 567. CD2C(CH3)2CF3 H CD3 CD3 568. CD2C(CH3)2CF3 CD3 CD3 CD3 569. H CD2C(CH3)2CF3 H H 570. CD3 CD2C(CH3)2CF3 H CD3 571. H CD2C(CH3)2CF3 CD3 H 572. H CD2C(CH3)2CF3 H CD3 573. CD3 CD2C(CH3)2CF3 CD3 H 574. CD3 CD2C(CH3)2CF3 H CD3 575. H CD2C(CH3)2CF3 CD3 CD3 576. CD3 CD2C(CH3)2CF3 CD3 CD3 577. H H CD2C(CH3)2CF3 H 578. CD3 H CD2C(CH3)2CF3 H 579. H CD3 CD2C(CH3)2CF3 H 580. H H CD2C(CH3)2CF3 CD3 581. CD3 CD3 CD2C(CH3)2CF3 H 582. CD3 H CD2C(CH3)2CF3 CD3 583. H CD3 CD2C(CH3)2CF3 CD3 584. CD3 CD3 CD2C(CH3)2CF3 CD3 585. CD2CH2CF3 H H H 586. CD2CH2CF3 CD3 H CD3 587. CD2CH2CF3 H CD3 H 588. CD2CH2CF3 H H CD3 589. CD2CH2CF3 CD3 CD3 H 590. CD2CH2CF3 CD3 H CD3 591. CD2CH2CF3 H CD3 CD3 592. CD2CH2CF3 CD3 CD3 CD3 593. H CD2CH2CF3 H H 594. CD3 CD2CH2CF3 H CD3 595. H CD2CH2CF3 CD3 H 596. H CD2CH2CF3 H CD3 597. CD3 CD2CH2CF3 CD3 H 598. CD3 CD2CH2CF3 H CD3 599. H CD2CH2CF3 CD3 CD3 600. CD3 CD2CH2CF3 CD3 CD3 601. H H CD2CH2CF3 H 602. CD3 H CD2CH2CF3 H 603. H CD3 CD2CH2CF3 H 604. H H CD2CH2CF3 CD3 605. CD3 CD3 CD2CH2CF3 H 606. CD3 H CD2CH2CF3 CD3 607. H CD3 CD2CH2CF3 CD3 608. CD3 CD3 CD2CH2CF3 CD3 609.
Figure US20170324049A1-20171109-C00915
 H H H 610.
Figure US20170324049A1-20171109-C00916
 CD3 H CD3 611.
Figure US20170324049A1-20171109-C00917
 H CD3 H 612.
Figure US20170324049A1-20171109-C00918
 H H CD3 613.
Figure US20170324049A1-20171109-C00919
 CD3 CD3 H 614.
Figure US20170324049A1-20171109-C00920
 CD3 H CD3 615.
Figure US20170324049A1-20171109-C00921
 H CD3 CD3 616.
Figure US20170324049A1-20171109-C00922
 CD3 CD3 CD3 617. H
Figure US20170324049A1-20171109-C00923
 H H 618. CD3
Figure US20170324049A1-20171109-C00924
 H CD3 619. H
Figure US20170324049A1-20171109-C00925
 CD3 H 620. H
Figure US20170324049A1-20171109-C00926
 H CD3 621. CD3
Figure US20170324049A1-20171109-C00927
 CD3 H 622. CD3
Figure US20170324049A1-20171109-C00928
 H CD3 623. H
Figure US20170324049A1-20171109-C00929
 CD3 CD3 624. CD3
Figure US20170324049A1-20171109-C00930
 CD3 CD3 625. H H
Figure US20170324049A1-20171109-C00931
 H 626. CD3 H
Figure US20170324049A1-20171109-C00932
 H 627. H CD3
Figure US20170324049A1-20171109-C00933
 H 628. H H
Figure US20170324049A1-20171109-C00934
 CD3 629. CD3 CD3
Figure US20170324049A1-20171109-C00935
 H 630. CD3 H
Figure US20170324049A1-20171109-C00936
 CD3 631. H CD3
Figure US20170324049A1-20171109-C00937
 CD3 632. CD3 CD3
Figure US20170324049A1-20171109-C00938
 CD3 633.
Figure US20170324049A1-20171109-C00939
 H H H 634.
Figure US20170324049A1-20171109-C00940
 CD3 H CD3 635.
Figure US20170324049A1-20171109-C00941
 H CD3 H 636.
Figure US20170324049A1-20171109-C00942
 H H CD3 637.
Figure US20170324049A1-20171109-C00943
 CD3 CD3 H 638.
Figure US20170324049A1-20171109-C00944
 CD3 H CD3 639.
Figure US20170324049A1-20171109-C00945
 H CD3 CD3 640.
Figure US20170324049A1-20171109-C00946
 CD3 CD3 CD3 641. H
Figure US20170324049A1-20171109-C00947
 H H 642. CH3
Figure US20170324049A1-20171109-C00948
 H CD3 643. H
Figure US20170324049A1-20171109-C00949
 CD3 H 644. H
Figure US20170324049A1-20171109-C00950
 H CD3 645. CD3
Figure US20170324049A1-20171109-C00951
 CD3 H 646. CD3
Figure US20170324049A1-20171109-C00952
 H CD3 647. H
Figure US20170324049A1-20171109-C00953
 CD3 CD3 648. CH3
Figure US20170324049A1-20171109-C00954
 CD3 CD3 649. H H
Figure US20170324049A1-20171109-C00955
 H 650. CD3 H
Figure US20170324049A1-20171109-C00956
 H 651. H CD3
Figure US20170324049A1-20171109-C00957
 H 652. H H
Figure US20170324049A1-20171109-C00958
 CD3 653. CD3 CD3
Figure US20170324049A1-20171109-C00959
 H 654. CD3 H
Figure US20170324049A1-20171109-C00960
 CD3 655. H CD3
Figure US20170324049A1-20171109-C00961
 CD3 656. CD3 CD3
Figure US20170324049A1-20171109-C00962
 CD3 657.
Figure US20170324049A1-20171109-C00963
 H H H 658.
Figure US20170324049A1-20171109-C00964
 CD3 H CD3 659.
Figure US20170324049A1-20171109-C00965
 H CD3 H 660.
Figure US20170324049A1-20171109-C00966
 H H CD3 661.
Figure US20170324049A1-20171109-C00967
 CD3 CD3 H 662.
Figure US20170324049A1-20171109-C00968
 CD3 H CD3 663.
Figure US20170324049A1-20171109-C00969
 H CD3 CD3 664.
Figure US20170324049A1-20171109-C00970
 CD3 CD3 CD3 665. H
Figure US20170324049A1-20171109-C00971
 H H 666. CD3
Figure US20170324049A1-20171109-C00972
 H CD3 667. H
Figure US20170324049A1-20171109-C00973
 CD3 H 668. H
Figure US20170324049A1-20171109-C00974
 H CD3 669. CD3
Figure US20170324049A1-20171109-C00975
 CD3 H 670. CD3
Figure US20170324049A1-20171109-C00976
 H CD3 671. H
Figure US20170324049A1-20171109-C00977
 CD3 CD3 672. CD3
Figure US20170324049A1-20171109-C00978
 CD3 CD3 673. H H
Figure US20170324049A1-20171109-C00979
 H 674. CD3 H
Figure US20170324049A1-20171109-C00980
 H 675. H CD3
Figure US20170324049A1-20171109-C00981
 H 676. H H
Figure US20170324049A1-20171109-C00982
 CD3 677. CD3 CD3
Figure US20170324049A1-20171109-C00983
 H 678. CD3 H
Figure US20170324049A1-20171109-C00984
 CD3 679. H CD3
Figure US20170324049A1-20171109-C00985
 CD3 680. CD3 CD3
Figure US20170324049A1-20171109-C00986
 CD3 681.
Figure US20170324049A1-20171109-C00987
 H H H 682.
Figure US20170324049A1-20171109-C00988
 CD3 H CD3 683.
Figure US20170324049A1-20171109-C00989
 H CD3 H 684.
Figure US20170324049A1-20171109-C00990
 H H CD3 685.
Figure US20170324049A1-20171109-C00991
 CD3 CD3 H 686.
Figure US20170324049A1-20171109-C00992
 CD3 H CD3 687.
Figure US20170324049A1-20171109-C00993
 H CD3 CD3 688.
Figure US20170324049A1-20171109-C00994
 CD3 CD3 CD3 689. H
Figure US20170324049A1-20171109-C00995
 H H 690. CD3
Figure US20170324049A1-20171109-C00996
 H CD3 691. H
Figure US20170324049A1-20171109-C00997
 CD3 H 692. H
Figure US20170324049A1-20171109-C00998
 H CD3 693. CD3
Figure US20170324049A1-20171109-C00999
 CD3 H 694. CD3
Figure US20170324049A1-20171109-C01000
 H CD3 695. H
Figure US20170324049A1-20171109-C01001
 CD3 CD3 696. CD3
Figure US20170324049A1-20171109-C01002
 CD3 CD3 697. H H
Figure US20170324049A1-20171109-C01003
 H 698. CD3 H
Figure US20170324049A1-20171109-C01004
 H 699. H CD3
Figure US20170324049A1-20171109-C01005
 H 700. H H
Figure US20170324049A1-20171109-C01006
 CD3 701. CD3 CD3
Figure US20170324049A1-20171109-C01007
 H 702. CD3 H
Figure US20170324049A1-20171109-C01008
 CD3 703. H CD3
Figure US20170324049A1-20171109-C01009
 CD3 704. CD3 CD3
Figure US20170324049A1-20171109-C01010
 CD3 705.
Figure US20170324049A1-20171109-C01011
 H H H 706.
Figure US20170324049A1-20171109-C01012
 CD3 H CD3 707.
Figure US20170324049A1-20171109-C01013
 H CD3 H 708.
Figure US20170324049A1-20171109-C01014
 H H CD3 709.
Figure US20170324049A1-20171109-C01015
 CD3 CD3 H 710.
Figure US20170324049A1-20171109-C01016
 CD3 H CD3 711.
Figure US20170324049A1-20171109-C01017
 H CD3 CD3 712.
Figure US20170324049A1-20171109-C01018
 CD3 CD3 CD3 713. H
Figure US20170324049A1-20171109-C01019
 H H 714. CD3
Figure US20170324049A1-20171109-C01020
 H CD3 715. H
Figure US20170324049A1-20171109-C01021
 CD3 H 716. H
Figure US20170324049A1-20171109-C01022
 H CD3 717. CD3
Figure US20170324049A1-20171109-C01023
 CD3 H 718. CD3
Figure US20170324049A1-20171109-C01024
 H CD3 719. H
Figure US20170324049A1-20171109-C01025
 CD3 CD3 720. CD3
Figure US20170324049A1-20171109-C01026
 CD3 CD3 721. H H
Figure US20170324049A1-20171109-C01027
 H 722. CD3 H
Figure US20170324049A1-20171109-C01028
 H 723. H CD3
Figure US20170324049A1-20171109-C01029
 H 724. H H
Figure US20170324049A1-20171109-C01030
 CD3 725. CD3 CD3
Figure US20170324049A1-20171109-C01031
 H 726. CD3 H
Figure US20170324049A1-20171109-C01032
 CD3 727. H CD3
Figure US20170324049A1-20171109-C01033
 CD3 728. CD3 CD3
Figure US20170324049A1-20171109-C01034
 CD3 729.
Figure US20170324049A1-20171109-C01035
 H H H 730.
Figure US20170324049A1-20171109-C01036
 CD3 H CD3 731.
Figure US20170324049A1-20171109-C01037
 H CD3 H 732.
Figure US20170324049A1-20171109-C01038
 H H CD3 733.
Figure US20170324049A1-20171109-C01039
 CH3 CH3 H 734.
Figure US20170324049A1-20171109-C01040
 CD3 H CD3 735.
Figure US20170324049A1-20171109-C01041
 H CD3 CD3 736.
Figure US20170324049A1-20171109-C01042
 CD3 CD3 CD3 737. H
Figure US20170324049A1-20171109-C01043
 H H 738. CD3
Figure US20170324049A1-20171109-C01044
 H CD3 739. H
Figure US20170324049A1-20171109-C01045
 CD3 H 740. H
Figure US20170324049A1-20171109-C01046
 H CD3 741. CD3
Figure US20170324049A1-20171109-C01047
 CD3 H 742. CD3
Figure US20170324049A1-20171109-C01048
 H CD3 743. H
Figure US20170324049A1-20171109-C01049
 CD3 CD3 744. CD3
Figure US20170324049A1-20171109-C01050
 CD3 CD3 745. H H
Figure US20170324049A1-20171109-C01051
 H 746. CD3 H
Figure US20170324049A1-20171109-C01052
 H 747. H CD3
Figure US20170324049A1-20171109-C01053
 H 748. H H
Figure US20170324049A1-20171109-C01054
 CH3 749. CD3 CD3
Figure US20170324049A1-20171109-C01055
 H 750. CD3 H
Figure US20170324049A1-20171109-C01056
 CD3 751. H CD3
Figure US20170324049A1-20171109-C01057
 CD3 752. CD3 CD3
Figure US20170324049A1-20171109-C01058
 CD3 753. CD(CH3)2 H CD2CH3 H 754. CD(CH3)2 H CD(CH3)2 H 755. CD(CH3)2 H CD2CH(CH3)2 H 756. CD(CH3)2 H C(CH3)3 H 757. CD(CH3)2 H CD2C(CH3)3 H 758. CD(CH3)2 H CD2CH2CF3 H 759. CD(CH3)2 H CD2C(CH3)2CF3 H 760. CD(CH3)2 H
Figure US20170324049A1-20171109-C01059
 H 761. CD(CH3)2 H
Figure US20170324049A1-20171109-C01060
 H 762. CD(CH3)2 H
Figure US20170324049A1-20171109-C01061
 H 763. CD(CH3)2 H
Figure US20170324049A1-20171109-C01062
 H 764. CD(CH3)2 H
Figure US20170324049A1-20171109-C01063
 H 765. CD(CH3)2 H
Figure US20170324049A1-20171109-C01064
 H 766. C(CH3)3 H CD2CH3 H 767. C(CH3)3 H CD(CH3)2 H 768. C(CH3)3 H CD2CH(CH3)2 H 769. C(CH3)3 H C(CH3)3 H 770. C(CH3)3 H CD2C(CH3)3 H 771. C(CH3)3 H CD2CH2CF3 H 772. C(CH3)3 H CD2C(CH3)2CF3 H 773. C(CH3)3 H
Figure US20170324049A1-20171109-C01065
 H 774. C(CH3)3 H
Figure US20170324049A1-20171109-C01066
 H 775. C(CH3)3 H
Figure US20170324049A1-20171109-C01067
 H 776. C(CH3)3 H
Figure US20170324049A1-20171109-C01068
 H 777. C(CH3)3 H
Figure US20170324049A1-20171109-C01069
 H 778. C(CH3)3 H
Figure US20170324049A1-20171109-C01070
 H 779. CD2C(CH3)3 H CD2CH3 H 780. CD2C(CH3)3 H CD(CH3)2 H 781. CD2C(CH3)3 H CD2CH(CH3)2 H 782. CD2C(CH3)3 H C(CH3)3 H 783. CD2C(CH3)3 H CD2C(CH3)3 H 784. CD2C(CH3)3 H CD2CH2CF3 H 785. CD2C(CH3)3 H CD2C(CH3)2CF3 H 786. CD2C(CH3)3 H
Figure US20170324049A1-20171109-C01071
 H 787. CD2C(CH3)3 H
Figure US20170324049A1-20171109-C01072
 H 788. CD2C(CH3)3 H
Figure US20170324049A1-20171109-C01073
 H 789. CD2C(CH3)3 H
Figure US20170324049A1-20171109-C01074
 H 790. CD2C(CH3)3 H
Figure US20170324049A1-20171109-C01075
 H 791. CD2C(CH3)3 H
Figure US20170324049A1-20171109-C01076
 H 792.
Figure US20170324049A1-20171109-C01077
 H CD2CH3 H 793.
Figure US20170324049A1-20171109-C01078
 H CD(CH3)2 H 794.
Figure US20170324049A1-20171109-C01079
 H CD2CH(CH3)2 H 795.
Figure US20170324049A1-20171109-C01080
 H C(CH3)3 H 796.
Figure US20170324049A1-20171109-C01081
 H CD2C(CH3)3 H 797.
Figure US20170324049A1-20171109-C01082
 H CD2CH2CF3 H 798.
Figure US20170324049A1-20171109-C01083
 H CD2C(CH3)2CF3 H 799.
Figure US20170324049A1-20171109-C01084
 H
Figure US20170324049A1-20171109-C01085
 H 800.
Figure US20170324049A1-20171109-C01086
 H
Figure US20170324049A1-20171109-C01087
 H 801.
Figure US20170324049A1-20171109-C01088
 H
Figure US20170324049A1-20171109-C01089
 H 802.
Figure US20170324049A1-20171109-C01090
 H
Figure US20170324049A1-20171109-C01091
 H 803.
Figure US20170324049A1-20171109-C01092
 H
Figure US20170324049A1-20171109-C01093
 H 804.
Figure US20170324049A1-20171109-C01094
 H
Figure US20170324049A1-20171109-C01095
 H 805.
Figure US20170324049A1-20171109-C01096
 H CD2CH3 H 806.
Figure US20170324049A1-20171109-C01097
 H CD(CH3)2 H 807.
Figure US20170324049A1-20171109-C01098
 H CD2CH(CH3)2 H 808.
Figure US20170324049A1-20171109-C01099
 H C(CH3)3 H 809.
Figure US20170324049A1-20171109-C01100
 H CD2C(CH3)3 H 810.
Figure US20170324049A1-20171109-C01101
 H CD2CH2CF3 H 811.
Figure US20170324049A1-20171109-C01102
 H CD2C(CH3)2CF3 H 812.
Figure US20170324049A1-20171109-C01103
 H
Figure US20170324049A1-20171109-C01104
 H 813.
Figure US20170324049A1-20171109-C01105
 H
Figure US20170324049A1-20171109-C01106
 H 814.
Figure US20170324049A1-20171109-C01107
 H
Figure US20170324049A1-20171109-C01108
 H 815.
Figure US20170324049A1-20171109-C01109
 H
Figure US20170324049A1-20171109-C01110
 H 816.
Figure US20170324049A1-20171109-C01111
 H
Figure US20170324049A1-20171109-C01112
 H 817.
Figure US20170324049A1-20171109-C01113
 H
Figure US20170324049A1-20171109-C01114
 H 818.
Figure US20170324049A1-20171109-C01115
 H CD2CH3 H 819.
Figure US20170324049A1-20171109-C01116
 H CD(CH3)2 H 820.
Figure US20170324049A1-20171109-C01117
 H CD2CH(CH3)2 H 821.
Figure US20170324049A1-20171109-C01118
 H C(CH3)3 H 822.
Figure US20170324049A1-20171109-C01119
 H CD2C(CH3)3 H 823.
Figure US20170324049A1-20171109-C01120
 H CD2CH2CF3 H 824.
Figure US20170324049A1-20171109-C01121
 H CD2C(CH3)2CF3 H 825.
Figure US20170324049A1-20171109-C01122
 H
Figure US20170324049A1-20171109-C01123
 H 826.
Figure US20170324049A1-20171109-C01124
 H
Figure US20170324049A1-20171109-C01125
 H 827.
Figure US20170324049A1-20171109-C01126
 H
Figure US20170324049A1-20171109-C01127
 H 828.
Figure US20170324049A1-20171109-C01128
 H
Figure US20170324049A1-20171109-C01129
 H 829.
Figure US20170324049A1-20171109-C01130
 H
Figure US20170324049A1-20171109-C01131
 H 830.
Figure US20170324049A1-20171109-C01132
 H
Figure US20170324049A1-20171109-C01133
 H 831.
Figure US20170324049A1-20171109-C01134
 H CD2CH3 H 832.
Figure US20170324049A1-20171109-C01135
 H CD(CH3)2 H 833.
Figure US20170324049A1-20171109-C01136
 H CD2CH(CH3)2 H 834.
Figure US20170324049A1-20171109-C01137
 H C(CH3)3 H 835.
Figure US20170324049A1-20171109-C01138
 H CD2C(CH3)3 H 836.
Figure US20170324049A1-20171109-C01139
 H CD2CH2CF3 H 837.
Figure US20170324049A1-20171109-C01140
 H CD2C(CH3)2CF3 H 838.
Figure US20170324049A1-20171109-C01141
 H
Figure US20170324049A1-20171109-C01142
 H 839.
Figure US20170324049A1-20171109-C01143
 H
Figure US20170324049A1-20171109-C01144
 H 840.
Figure US20170324049A1-20171109-C01145
 H
Figure US20170324049A1-20171109-C01146
 H 841.
Figure US20170324049A1-20171109-C01147
 H
Figure US20170324049A1-20171109-C01148
 H 842.
Figure US20170324049A1-20171109-C01149
 H
Figure US20170324049A1-20171109-C01150
 H 843.
Figure US20170324049A1-20171109-C01151
 H
Figure US20170324049A1-20171109-C01152
 H 844.
Figure US20170324049A1-20171109-C01153
 H CD2CH3 H 845.
Figure US20170324049A1-20171109-C01154
 H CD(CH3)2 H 846.
Figure US20170324049A1-20171109-C01155
 H CD2CH(CH3)2 H 847.
Figure US20170324049A1-20171109-C01156
 H C(CH3)3 H 848.
Figure US20170324049A1-20171109-C01157
 H CD2C(CH3)3 H 849.
Figure US20170324049A1-20171109-C01158
 H CD2CH2CF3 H 850.
Figure US20170324049A1-20171109-C01159
 H CD2C(CH3)2CF3 H 851.
Figure US20170324049A1-20171109-C01160
 H
Figure US20170324049A1-20171109-C01161
 H 852.
Figure US20170324049A1-20171109-C01162
 H
Figure US20170324049A1-20171109-C01163
 H 853.
Figure US20170324049A1-20171109-C01164
 H
Figure US20170324049A1-20171109-C01165
 H 854.
Figure US20170324049A1-20171109-C01166
 H
Figure US20170324049A1-20171109-C01167
 H 855.
Figure US20170324049A1-20171109-C01168
 H
Figure US20170324049A1-20171109-C01169
 H 856.
Figure US20170324049A1-20171109-C01170
 H
Figure US20170324049A1-20171109-C01171
 H
8. The compound of claim 7, wherein the compound is the Compound x having the Formula Ir(LAi)(LBj)2;
wherein x=856i+j−856; i is an integer from 1 to 111; and j is an integer from 1 to 856;
wherein LA is selected from the group consisting of:
Figure US20170324049A1-20171109-C01172
Figure US20170324049A1-20171109-C01173
Figure US20170324049A1-20171109-C01174
Figure US20170324049A1-20171109-C01175
Figure US20170324049A1-20171109-C01176
Figure US20170324049A1-20171109-C01177
Figure US20170324049A1-20171109-C01178
Figure US20170324049A1-20171109-C01179
Figure US20170324049A1-20171109-C01180
Figure US20170324049A1-20171109-C01181
Figure US20170324049A1-20171109-C01182
Figure US20170324049A1-20171109-C01183
Figure US20170324049A1-20171109-C01184
Figure US20170324049A1-20171109-C01185
Figure US20170324049A1-20171109-C01186
Figure US20170324049A1-20171109-C01187
Figure US20170324049A1-20171109-C01188
Figure US20170324049A1-20171109-C01189
Figure US20170324049A1-20171109-C01190
Figure US20170324049A1-20171109-C01191
Figure US20170324049A1-20171109-C01192
Figure US20170324049A1-20171109-C01193
9. An organic light-emitting device (OLED) comprising:
an anode;
a cathode; and
an organic layer, disposed between the anode and the cathode, comprising a compound having the structure of (LA)nIr(LB)3-n represented by Formula I:
Figure US20170324049A1-20171109-C01194
wherein R2, R3, R4 and R5 each represent monosubstitution, disubstitution, trisubstitution, tetrasubstitution, or no substitution;
wherein R1 is an aryl or heteroaryl containing at least one group selected from group A consisting of:
Figure US20170324049A1-20171109-C01195
Figure US20170324049A1-20171109-C01196
Figure US20170324049A1-20171109-C01197
wherein R1 can be further substituted with one or more substituents selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, and combinations thereof;
wherein R2, R3, R4, and R5 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, and combinations thereof; and
wherein n is 1 or 2.
10. The OLED of claim 9, wherein the organic layer is an emissive layer and the compound is an emissive dopant or a non-emissive dopant.
11. The OLED of claim 9, wherein the organic layer further comprises a host, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan;
wherein any substituent in the host 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, CnH2n-Ar1, or no substitution;
wherein n is between 1 and 10; and
wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
12. The OLED of claim 9, wherein the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, aza-triphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene
13. The OLED of claim 9, wherein the organic layer further comprises a host, wherein the host is selected from the group consisting of:
Figure US20170324049A1-20171109-C01198
Figure US20170324049A1-20171109-C01199
Figure US20170324049A1-20171109-C01200
Figure US20170324049A1-20171109-C01201
Figure US20170324049A1-20171109-C01202
and combinations thereof.
14. The OLED of claim 9, wherein the organic layer further comprises a host, wherein the host comprises a metal complex.
15. A consumer product comprising an organic light-emitting device (OLED) comprising:
an anode;
a cathode; and
an organic layer, disposed between the anode and the cathode, comprising a compound having the structure of (LA)nIr(LB)3-n represented by Formula I:
Figure US20170324049A1-20171109-C01203
wherein R2, R3, R4 and R5 each represent monosubstitution, disubstitution, trisubstitution, tetrasubstitution, or no substitution;
wherein R1 is an aryl or heteroaryl containing at least one group selected from group A consisting of:
Figure US20170324049A1-20171109-C01204
Figure US20170324049A1-20171109-C01205
Figure US20170324049A1-20171109-C01206
wherein R1 can be further substituted with one or more substituents selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, and combinations thereof;
wherein R2, R3, R4, and R5 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, and combinations thereof; and
wherein n is 1 or 2.
16. The consumer product of claim 15, wherein the consumer product is selected from the group consisting of a flat panel display, a computer monitor, a medical monitors television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, and a sign.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180287078A1 (en) * 2014-04-14 2018-10-04 Universal Display Corporation Organic Electroluminescent Materials and Devices
US10211399B2 (en) * 2016-10-11 2019-02-19 Wuhan China Star Optoelectronics Technology Co., Ltd. Transparent OLED display and manufacturing method thereof
US10825998B2 (en) 2014-04-14 2020-11-03 Universal Display Corporation Organic electroluminescent materials and devices

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070196691A1 (en) * 2006-02-20 2007-08-23 Dai Ikemizu Organic electroluminescent element, white light emission element, full color display device and lighting device
US20090230850A1 (en) * 2005-10-11 2009-09-17 Konica Minolta Holdings, Inc. Electroluminescent element, liquid crystal display and illuminating device
US20100141127A1 (en) * 2008-11-11 2010-06-10 Universal Display Corporation Phosphorescent emitters
US20110204333A1 (en) * 2010-02-25 2011-08-25 Universal Display Corporation Phosphorescent emitters
US20130270541A1 (en) * 2011-01-07 2013-10-17 Idemitsu Kosan Co., Ltd. Imidazole compound production method, imidazole compound, imidazole-based compound, organic metal complex, material for organic electroluminescent element, organic electroluminescent element, display device, and lighting device
US20140054563A1 (en) * 2012-08-24 2014-02-27 Universal Display Corporation Phosphorescent emitters with phenylimidazole ligands

Family Cites Families (133)

* 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
DE69412567T2 (en) 1993-11-01 1999-02-04 Hodogaya Chemical Co., Ltd., Tokio/Tokyo Amine compound and electroluminescent device containing it
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
US6013982A (en) 1996-12-23 2000-01-11 The Trustees Of Princeton University Multicolor display devices
US6091195A (en) 1997-02-03 2000-07-18 The Trustees Of Princeton University Displays having mesa pixel configuration
US5834893A (en) 1996-12-23 1998-11-10 The Trustees Of Princeton University High efficiency organic light emitting devices with light directing structures
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
CN101924190B (en) 2000-08-11 2012-07-04 普林斯顿大学理事会 Organometallic compounds and emission-shifting organic electrophosphorescence
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
CN100440568C (en) 2001-06-20 2008-12-03 昭和电工株式会社 Light-emitting materials and organic light-emitting devices
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 electron transport and organic light emitting device 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
KR100686268B1 (en) 2002-08-27 2007-02-28 후지필름 가부시키가이샤 Organometallic Complex, Organic EL Element, and Organic EL Display
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
EP1606296B1 (en) 2003-03-24 2009-08-05 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
JP4673744B2 (en) 2003-05-29 2011-04-20 新日鐵化学株式会社 Organic electroluminescence device
WO2004111066A1 (en) 2003-06-09 2004-12-23 Hitachi Chemical Co., Ltd. Metal coordination compound, polymer composition, and organic electroluminescence element using them
JP2005011610A (en) 2003-06-18 2005-01-13 Nippon Steel Chem Co Ltd Organic electroluminescence device
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
WO2005089024A1 (en) 2004-03-11 2005-09-22 Mitsubishi Chemical Corporation 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
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
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
WO2005123873A1 (en) 2004-06-17 2005-12-29 Konica Minolta Holdings, Inc. Organic electroluminescent device material, organic electroluminescent device, display and illuminating device
CA2568667A1 (en) 2004-06-28 2006-01-05 Ciba Specialty Chemicals Holding Inc. Electroluminescent metal complexes with triazoles and benzotriazoles
US20060008670A1 (en) 2004-07-06 2006-01-12 Chun Lin Organic light emitting materials and devices
EP2178348B1 (en) 2004-07-23 2012-11-21 Konica Minolta Holdings, Inc. Organic electroluminescent element, display and illuminator
DE102004057072A1 (en) 2004-11-25 2006-06-01 Basf Ag Use of Transition Metal Carbene Complexes in Organic Light Emitting Diodes (OLEDs)
KR101272435B1 (en) 2004-12-30 2013-06-07 이 아이 듀폰 디 네모아 앤드 캄파니 Organometallic complexes
GB2437453B (en) 2005-02-04 2011-05-04 Konica Minolta Holdings Inc Material for organic electroluminescence element, organic electroluminescence element, display device and lighting device
KR100803125B1 (en) 2005-03-08 2008-02-14 엘지전자 주식회사 Red phosphorescent compound and organic light emitting device 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
JPWO2006103874A1 (en) 2005-03-29 2008-09-04 コニカミノルタホールディングス株式会社 ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING 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
US9051344B2 (en) 2005-05-06 2015-06-09 Universal Display Corporation Stability OLED materials and devices
JP4533796B2 (en) 2005-05-06 2010-09-01 富士フイルム株式会社 Organic electroluminescence device
CN101203583A (en) 2005-05-31 2008-06-18 通用显示公司 Benzo [9,10] phenanthrene matrices in phosphorescent emitting diodes
WO2006132173A1 (en) 2005-06-07 2006-12-14 Nippon Steel Chemical Co., Ltd. Organic metal complex and organic electroluminescent device using same
US7638072B2 (en) 2005-06-27 2009-12-29 E. I. Du Pont De Nemours And Company Electrically conductive polymer compositions
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
KR20080085000A (en) 2005-12-01 2008-09-22 신닛테츠가가쿠 가부시키가이샤 Organic electroluminescent device
EP1956022B1 (en) 2005-12-01 2012-07-25 Nippon Steel Chemical Co., Ltd. Compound for organic electroluminescent element and organic electroluminescent element
KR101600624B1 (en) 2006-02-10 2016-03-21 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
KR101453109B1 (en) 2006-04-26 2014-10-27 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
CN101461074B (en) 2006-06-02 2011-06-15 出光兴产株式会社 Material for organic electroluminescence element and organic electroluminescence element using same
JP5139297B2 (en) 2006-08-23 2013-02-06 出光興産株式会社 Aromatic amine derivatives and organic electroluminescence devices using them
JP5589251B2 (en) 2006-09-21 2014-09-17 コニカミノルタ株式会社 Organic electroluminescence element material
JP5099013B2 (en) 2006-10-13 2012-12-12 コニカミノルタホールディングス株式会社 ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE
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
US20080102223A1 (en) 2006-11-01 2008-05-01 Sigurd Wagner Hybrid layers for use in coatings on electronic devices or other articles
US8062769B2 (en) 2006-11-09 2011-11-22 Nippon Steel Chemical Co., Ltd. Indolocarbazole compound for use in organic electroluminescent device and organic electroluminescent device
WO2008062636A1 (en) 2006-11-24 2008-05-29 Idemitsu Kosan Co., Ltd. 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
WO2008101842A1 (en) 2007-02-23 2008-08-28 Basf Se Electroluminescent metal complexes with benzotriazoles
EP2150556B1 (en) 2007-04-26 2011-01-12 Basf Se Silanes containing phenothiazine-s-oxide or phenothiazine-s,s-dioxide groups and the use thereof in oleds
WO2008156879A1 (en) 2007-06-20 2008-12-24 Universal Display Corporation Blue phosphorescent imidazophenanthridine materials
CN101720330B (en) 2007-06-22 2017-06-09 Udc爱尔兰有限责任公司 Light emitting cu (I) complex compound
US8373159B2 (en) 2007-07-05 2013-02-12 Basf Se Organic light-emitting diodes comprising carbene-transition metal complex emitter, and at least one compound selected from disilylcarbazoles, disilyldibenzofurans, disilyldibenzothiophenes, disilyldibenzophospholes, disilyldibenzothiophene s-oxides and disilyldibe
JP5473600B2 (en) 2007-07-07 2014-04-16 出光興産株式会社 Chrysene derivative and organic electroluminescence device using the same
US8779655B2 (en) 2007-07-07 2014-07-15 Idemitsu Kosan Co., Ltd. Organic electroluminescence device and material for organic electroluminescence device
WO2009008205A1 (en) 2007-07-07 2009-01-15 Idemitsu Kosan Co., Ltd. Organic electroluminescent device and material for organic electroluminescent device
WO2009008201A1 (en) 2007-07-07 2009-01-15 Idemitsu Kosan Co., Ltd. Naphthalene derivative, material for organic el element, and organic el element using the material
US20090045731A1 (en) 2007-07-07 2009-02-19 Idemitsu Kosan Co., Ltd. Organic electroluminescence device and material for organic electroluminescence device
TW200903877A (en) 2007-07-10 2009-01-16 Idemitsu Kosan Co Material for organic electroluminescence device and organic electroluminescence device utilizing the same
US8080658B2 (en) 2007-07-10 2011-12-20 Idemitsu Kosan Co., Ltd. Material for organic electroluminescent element and organic electroluminescent element employing the same
CN101688052A (en) 2007-07-27 2010-03-31 E.I.内穆尔杜邦公司 Aqueous dispersion of conductive polymer comprising inorganic nanoparticles
EP2185532B1 (en) 2007-08-08 2016-11-09 Universal Display Corporation Benzo-fused thiophene compounds comprising a triphenylene group
JP2009040728A (en) 2007-08-09 2009-02-26 Canon Inc Organometallic complex and organic light emitting device using the same
JP2011500648A (en) 2007-10-17 2011-01-06 ビーエーエスエフ ソシエタス・ヨーロピア 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
WO2009063833A1 (en) 2007-11-15 2009-05-22 Idemitsu Kosan Co., Ltd. Benzochrysene derivative and organic electroluminescent device using the same
EP2221896A4 (en) 2007-11-22 2012-04-18 Idemitsu Kosan Co ORGANIC EL ELEMENT
US8574725B2 (en) 2007-11-22 2013-11-05 Idemitsu Kosan Co., Ltd. Organic el element and solution containing organic el material
WO2009073245A1 (en) 2007-12-06 2009-06-11 Universal Display Corporation Light-emitting organometallic complexes
WO2009085344A2 (en) 2007-12-28 2009-07-09 Universal Display Corporation Dibenzothiophene-containing materials in phosphorescent light emitting diodes
US8221905B2 (en) 2007-12-28 2012-07-17 Universal Display Corporation Carbazole-containing materials in phosphorescent light emitting diodes
KR101691610B1 (en) 2008-02-12 2017-01-02 유디씨 아일랜드 리미티드 Electroluminescent metal complexes with dibenzo[f,h]quinoxalines
KR101833658B1 (en) 2008-05-07 2018-02-28 더 트러스티즈 오브 프린스턴 유니버시티 Hybrid layers for use in coatings on electronic devices or other articles
JP5707665B2 (en) 2008-12-03 2015-04-30 コニカミノルタ株式会社 ORGANIC ELECTROLUMINESCENCE ELEMENT, LIGHTING DEVICE AND DISPLAY DEVICE HAVING THE ELEMENT
US8709615B2 (en) 2011-07-28 2014-04-29 Universal Display Corporation Heteroleptic iridium complexes as dopants
US8722205B2 (en) 2009-03-23 2014-05-13 Universal Display Corporation Heteroleptic iridium complex
US8795850B2 (en) 2011-05-19 2014-08-05 Universal Display Corporation Phosphorescent heteroleptic phenylbenzimidazole dopants and new synthetic methodology
US9212197B2 (en) 2011-05-19 2015-12-15 Universal Display Corporation Phosphorescent heteroleptic phenylbenzimidazole dopants
US9193745B2 (en) 2011-11-15 2015-11-24 Universal Display Corporation Heteroleptic iridium complex
JP2013245179A (en) 2012-05-25 2013-12-09 Konica Minolta Inc Metal complex, organic electroluminescent element, display and illumination apparatus
US10400163B2 (en) * 2013-02-08 2019-09-03 Universal Display Corporation Organic electroluminescent materials and devices

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090230850A1 (en) * 2005-10-11 2009-09-17 Konica Minolta Holdings, Inc. Electroluminescent element, liquid crystal display and illuminating device
US20070196691A1 (en) * 2006-02-20 2007-08-23 Dai Ikemizu Organic electroluminescent element, white light emission element, full color display device and lighting device
US20100141127A1 (en) * 2008-11-11 2010-06-10 Universal Display Corporation Phosphorescent emitters
US20110204333A1 (en) * 2010-02-25 2011-08-25 Universal Display Corporation Phosphorescent emitters
US20130270541A1 (en) * 2011-01-07 2013-10-17 Idemitsu Kosan Co., Ltd. Imidazole compound production method, imidazole compound, imidazole-based compound, organic metal complex, material for organic electroluminescent element, organic electroluminescent element, display device, and lighting device
US20140054563A1 (en) * 2012-08-24 2014-02-27 Universal Display Corporation Phosphorescent emitters with phenylimidazole ligands

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180287078A1 (en) * 2014-04-14 2018-10-04 Universal Display Corporation Organic Electroluminescent Materials and Devices
US10825998B2 (en) 2014-04-14 2020-11-03 Universal Display Corporation Organic electroluminescent materials and devices
US11005052B2 (en) * 2014-04-14 2021-05-11 Universal Display Corporation Organic electroluminescent materials and devices
US11793066B2 (en) 2014-04-14 2023-10-17 Universal Display Corporation Organic electroluminescent materials and devices
US10211399B2 (en) * 2016-10-11 2019-02-19 Wuhan China Star Optoelectronics Technology Co., Ltd. Transparent OLED display and manufacturing method thereof

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