Organic electroluminescent materials and devices

Abstract

To provide novel organometallic complexes having bis- or tris-heteroleptic ligands and a large aspect ratio in one direction, and their use in OLEDs to enhance efficiency.SOLUTION: Provided is an OLED material represented by Formula III. (In the formula, rings A, B, C, and D are 5- or 6-membered carbon rings or heterocycles, L1-L4 are direct bond, BR, NR, PR, O, S, Se, C=O, S=O, etc., Q1-Q4 are selected from the group consisting of direct bond and oxygen, Z1-Z4 are carbon or nitrogen, and M2 represents Pt or Pd).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This application claims priority under 35 U.S.C. §119(e)(1) to U.S. Provisional Application No. 62 / 516,329, filed June 7, 2017, U.S. Provisional Application No. 62 / 352,139, filed June 20, 2016, U.S. Provisional Application No. 62 / 450,848, filed January 26, 2017, U.S. Provisional Application No. 62 / 479,795, filed March 31, 2017, and U.S. Provisional Application No. 62 / 480,746, filed April 3, 2017, the disclosures of which are incorporated by reference in their entireties.

[0002] The present disclosure relates to compounds for use as phosphorescent emitters and devices, such as organic light-emitting diodes, that include said compounds. More specifically, the present disclosure relates to organometallic complexes that have a larger aspect ratio in one direction to enhance efficiency and their use in OLEDs. [Background technology]

[0003] Optoelectronic devices utilizing organic materials are becoming increasingly desirable for several reasons. Because many of the materials used to fabricate such devices are relatively inexpensive, organic optoelectronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as flexibility, may make them well suited for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic light-emitting layer emits light can generally be easily tuned with appropriate dopants.

[0004] OLEDs utilize thin organic films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Patent Nos. 5,623,999; 5,723,999; and 5,723,999, which are incorporated herein by reference in their entireties.

[0005] One application of phosphorescent emissive molecules is full-color displays. Industry standards for such displays require pixels adapted to emit specific colors, referred to as "saturated" colors. In particular, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. Conventionally, liquid crystal display emission from a white backlight is filtered with absorbing filters to produce red, green, and blue emission. Similar techniques can be used with OLEDs. White OLEDs can be either single EML devices or stacked structures. Color can be measured using CIE coordinates, which are well known in the art.

[0006] An example of a green emitting molecule has the following structure: [ka] The compound is tris(2-phenyl)iridium, denoted as Ir(ppy)3, having the formula:

[0007] In this figure and later figures herein, we depict the coordination bond from nitrogen to the metal (here Ir) as a straight line.

[0008] As used herein, the term "organic" includes polymeric and small molecule organic materials that can be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecules" can actually be quite large. Small molecules can contain repeating 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 can be incorporated into polymers, for example, as pendant groups on a polymer backbone or as part of the backbone. Small molecules can also serve as the core moiety of dendrimers, which consist of a series of chemical shells built on the core moiety. The core moiety of a dendrimer can be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be "small molecules," and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

[0009] As used herein, "top" means furthest from the substrate, while "bottom" means closest to the substrate. When a first layer is described as "disposed over" a second layer, the first layer is disposed further from the substrate. There may be other layers between the first and second layers, 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 may be various organic layers in between.

[0010] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium, either in the form of a solution or suspension.

[0011] A ligand may be referred to as "photoactive" if it is considered to directly contribute to the photoactive properties of the emissive material. A ligand may be referred to as "ancillary" if it is considered not to contribute to the photoactive properties of the emissive material, although the ancillary ligand may modify the properties of the photoactive ligand.

[0012] As used herein, and as would generally be understood by one of ordinary skill 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. Because ionization potentials (IPs) are measured as negative energies relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (a less negative EA). 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.

[0013] As used herein, and as will generally be understood by those 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 being farther 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.

[0014] Further details on OLEDs and the above definitions can be found in US Pat. No. 6,223,999, which is incorporated herein by reference in its entirety. Summary of the Invention

[0015] The present disclosure also includes compounds of the present invention.

[0016] According to another aspect, an OLED is disclosed, comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising a compound represented by Formula I:

[0017] According to another aspect, a consumer product is disclosed that includes an OLED, the OLED including an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer including a compound represented by Formula I.

[0018] Compositions comprising compounds of Formula I are also disclosed. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 1 shows an organic light-emitting device.

[0020] [Figure 2] FIG. 2 shows an inverted organic light-emitting device that does not have a separate electron transport layer. DETAILED DESCRIPTION OF THE INVENTION

[0021] 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 migrate to the oppositely charged electrode, respectively. When an electron and hole localize on the same molecule, an "exciton," a localized electron-hole pair with an excited energy state, is formed. Light is emitted via a photoemissive mechanism when the exciton relaxes. In some cases, the exciton may be localized on an excimer or exciplex. Non-radiative mechanisms, such as thermal relaxation, can also occur but are generally considered undesirable.

[0022] Early OLEDs used emissive molecules that emitted light from their singlet state ("fluorescence"), as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in a time frame of less than 10 nanoseconds.

[0023] More recently, OLEDs have been demonstrated that have emissive materials that emit light from triplet states ("phosphorescence"). Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Vol. 395, No. 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light emitting devices based on electrophosphorescence," Appl. Phys. Lett., Vol. 75, No. 3, 4-6 (1999) ("Baldo-II"), which are incorporated by reference in their entireties. Phosphorescence is described in further detail in U.S. Pat. No. 7,279,704, columns 5-6, which are incorporated by reference.

[0024] FIG. 1 shows an organic light-emitting device 100. The drawing is not necessarily 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 further detail in U.S. Pat. No. 7,279,704, cols. 6-10, which is incorporated by reference.

[0025] Further examples are available for each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole-transporting 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. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron-transporting 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. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes, including composite cathodes having a thin layer of metal, such as Mg:Ag, with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use of blocking layers are described in more detail in U.S. Patent 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 can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0026] 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 can be fabricated by depositing the layers described, in order. Because the most common OLED configuration has the cathode disposed above the anode, and device 200 has cathode 215 disposed below anode 230, device 200 is sometimes 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 an example of how some layers can be omitted from the structure of device 100.

[0027] The simple layer structures illustrated in Figures 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the present invention can be used in conjunction 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. A functional OLED may be achieved by combining the various layers described in various 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. While many of the examples provided herein describe various layers as including a single material, it is understood that combinations of materials, such as mixtures of hosts and dopants, or more generally, mixtures, may be used. Layers may also 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. The organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials, for example, as described with respect to Figures 1 and 2.

[0028] Structures and materials not specifically described may also be used, such as OLEDs (PLEDs) composed of polymeric materials, such as those disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. As a further example, an OLED 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. OLED structures may deviate from the simple layered structures illustrated in FIGS. 1 and 2. For example, the substrate may include angled reflective surfaces to improve outcoupling, such as mesa structures as described in U.S. Pat. No. 6,091,195 to Forrest et al. and / or recessed structures as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0029] Unless otherwise specified, any of the layers of the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include deposition by thermal evaporation, such as those described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties; inkjet deposition; organic vapor phase deposition (OVPD), such as that described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety; and organic vapor jet printing (OVJP), such as that 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 performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition via masks, such as those described in U.S. Patent Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, deposition via cold welding, and patterning associated with some deposition methods, such as inkjet and OVJD. Other methods may also be used. The material to be deposited may be modified to be compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least three carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents with 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. Materials with asymmetric structures may have better solution processability than those with symmetric structures, because asymmetric materials may be less prone to recrystallization. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

[0030] Devices fabricated according to embodiments of the present invention may further include 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, vapors, and / or gases. The barrier layer may be deposited over, under, or adjacent to the substrate, the electrode, or any other portion of the device, including the edges. The barrier layer may include 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 and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds, or both. Preferred barrier layers include mixtures of polymeric and non-polymeric materials, as described in U.S. Pat. No. 7,968,146 and PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entireties. To be considered a "mixture," the polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and / or simultaneously. The weight ratio of polymeric to non-polymeric materials can be in the range of 95:5 to 5:95. The polymeric and non-polymeric materials can be made from the same precursor materials. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

[0031] Devices made in accordance with embodiments of the present invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into various electronic products or intermediate components. 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 end-user product manufacturers. Such electronic component modules can optionally include drive electronics and / or power sources. Devices made in accordance with embodiments of the present invention can be incorporated into a wide variety of consumer products that have one or more electronic component modules (or units) incorporated therein. Such consumer products include any type of product that includes one or more light sources and / or one or more display devices of some kind. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor illumination and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, cars, video walls including multiple displays aligned together, theater or stadium screens, and signage. A variety of control mechanisms, including passive matrix and active matrix, can be used to control devices made in accordance with the present invention. Many of the devices are intended for use within a temperature range comfortable to humans, such as 18°C ​​to 30°C, and more preferably room temperature (20-25°C), but they can also be used outside this temperature range, e.g., between -40°C and +80°C.

[0032] 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 use the materials and structures. More generally, organic devices such as organic transistors may use the materials and structures.

[0033] As used herein, the terms "halo," "halogen," or "halide" include fluorine, chlorine, bromine, and iodine.

[0034] As used herein, the term "alkyl" refers to both straight-chain and branched-chain alkyl groups. Preferred alkyl groups contain 1 to 15 carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, and 2,2-dimethylpropyl. Furthermore, the alkyl groups may be optionally substituted.

[0035] As used herein, the term "cycloalkyl" refers to a cyclic alkyl group. Preferred cycloalkyl groups contain 3 to 10 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, and adamantyl. Furthermore, the cycloalkyl groups may be substituted.

[0036] As used herein, the term "alkenyl" refers to both straight-chain and branched-chain alkenyl groups. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkenyl groups may be substituted.

[0037] As used herein, the term "alkynyl" refers to both straight-chain and branched-chain alkyne groups. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkynyl groups may be substituted.

[0038] As used herein, the terms "aralkyl" and "arylalkyl" are used interchangeably and refer to an alkyl group having an aromatic group as a substituent. Additionally, the aralkyl group may be optionally substituted.

[0039] As used herein, the term "heterocyclic group" refers to aromatic and non-aromatic ring groups. Heteroaromatic ring groups also refer to heteroaryl. Preferred heteroaromatic ring groups contain 3 to 7 ring atoms and at least one heteroatom, and include cyclic amines such as morpholino, piperidino, and pyrrolidino, and cyclic ethers such as tetrahydrofuran and tetrahydropyran. Furthermore, the heterocyclic group may be substituted.

[0040] As used herein, the term "aryl" or "aromatic group" refers to monocyclic and polycyclic ring systems. A polycyclic ring can have two or more rings in which two carbon atoms are shared by two adjacent rings (the rings are "fused"), at least one of which is aromatic, e.g., the other rings are cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups contain 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Aryl groups having 6 carbon atoms, 10 carbon atoms, or 12 carbon atoms are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, with phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene being preferred. Furthermore, the aryl group may be substituted.

[0041] As used herein, the term "heteroaryl" refers to a monocyclic heteroaromatic group that can contain 1 to 5 heteroatoms. The term heteroaryl also includes polycyclic heteroaromatic systems having two or more rings in which two atoms are shared by two adjacent rings (the rings are "fused"), at least one of which is heteroaryl, and the other rings can be, for example, cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 12 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, benziso ... Examples of heteroaryl groups include benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, and preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and their aza analogs. Furthermore, the heteroaryl group may be optionally substituted.

[0042] The alkyl, the cycloalkyl, the alkenyl, the alkynyl, the aralkyl, the heterocycle, the aryl, and the heteroaryl may be unsubstituted or substituted with one or more substituents selected from 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.

[0043] As used herein, "substituted" indicates that a substituent other than H is attached to the relevant position, such as a carbon. Thus, for example, R 1 is monosubstituted, R 1 must be other than H. Similarly, R 1 is disubstituted, R 1 Two of the must be other than H. Similarly, R 1 is unsubstituted, R 1 is hydrogen at all substitution positions.

[0044] The term "aza" in the fragments described herein, such as aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the C—H groups in each fragment can be replaced with a nitrogen atom; for example, but not by way of limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Those skilled in the art can easily imagine other nitrogen analogs of the above-described aza derivatives, and all such analogs are intended to be encompassed by the terms described herein.

[0045] It is understood that when a molecular fragment is described as a substituent or as being attached to another moiety, the name may be described as either the fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (benzene, naphthalene, dibenzofuran). Different designations of substituents or attached fragments are considered equivalent herein.

[0046] This disclosure provides organometallic complexes based on Ir, Os, Rh, Ru, Re, Pt, or Pd, which have bis- or tris-heteroleptic ligands and large aspect ratios in one direction. The inventors have discovered that incorporating such compounds into OLEDs enhances device efficiency. The ligands are arranged so that the molecular length in one direction is longer than in any other direction, thereby resulting in a large aspect ratio. These compounds with large aspect ratios exhibit enhanced external quantum efficiency (EQE) when applied as emitters in PhOLED devices. This is because the compounds preferentially orient in a horizontal orientation relative to the plane of the substrate (i.e., parallel to the substrate), thereby maximizing light extraction from the emitter compound. The horizontal orientation maximizes the surface area of ​​the emitter molecules facing the emitting front of the device. Some examples of organometallic compounds disclosed herein have three different bidentate cyclometallated ligands coordinated to the iridium metal center. Some other examples of organometallic compounds have two different bidentate cyclometallating ligands coordinated to the platinum metal center.

[0047] According to an aspect of the present disclosure, a compound represented by a formula selected from the group consisting of: [ka] wherein ring A, ring B, ring C, ring D, ring E, and ring F are each a 5- or 6-membered carbocyclic or heterocyclic ring; In Formula I: AB, CD, and EF are metals M 1and forming three bidentate ligands coordinated with; AB, CD, and EF are different from one another; in the octahedral coordination configuration, ring A is trans to ring D, ring B is trans to ring E, and ring C is trans to ring F; In Formula II: AB, CD, and one acetylacetonate ligand are linked to a metal M 1 and form three bidentate ligands coordinated with; AB and CD are different from one another; in the octahedral coordination configuration, ring A is trans to ring D, ring B is trans to the oxygen atom, and ring C is trans to the oxygen atom; In Formula III: L 1 and L 3 are each independently selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO, CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; n1 and n2 are each independently 0 or 1; when n1 or n2 is 1, L 2 or L 4 is selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO, CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; when n1 or n2 is 0, L 2 or L 4 does not exist;Q 1 , Q 2 , Q 3 , and Q 4 are each independently selected from the group consisting of a direct bond and oxygen; Z 1 , Z 2 , Z 3 , and Z 4 If any of the Qs is nitrogen, they will be bonded to 1 , Q 2 , Q 3 , and Q 4 is a direct bond; In a square planar configuration, ring A is trans to ring D and ring B is trans to ring C; R 1 , R 2 , R 3 , R4 , R 5 , R 6 , and R 7 represents the maximum number of substitutions possible, from mono-substitution to no substitution, respectively; Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , and Z 6 are each independently selected from the group consisting of carbon and nitrogen; M 1 is a metal selected from the group consisting of Ir, Os, Rh, Ru, and Re; M 2 is a metal selected from the group consisting of Pt and Pd; The first distance is M 1 The R that is furthest away from 1 Atoms in and M 1 The R that is furthest away from 4 is the distance between the atoms in The second distance is M 1 The R that is furthest away from 2 Atoms in and M 1 The R that is furthest away from 5 is the distance between the atoms in The third distance is M 1 The R that is furthest away from 3 Atoms in and M 1 The R that is furthest away from 6 is the distance between the atoms in The fourth distance is M 2 The R that is furthest away from 1 Atoms in and M 2 The R that is furthest away from 4 is the distance between the atoms in The fifth distance is M 2 The R that is furthest away from 2 Atoms in and R 3 M inside 2 The R that is furthest away from 3 is the distance between the atoms in the first distance is greater than the second distance and the third distance by at least 1.5 Å; the fourth distance is at least 1.5 Å greater than the fifth distance; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Any two substituents in may be bonded or fused to form a ring. The 1.5 Å mentioned above is the distance of the CC bond (i.e., adding the methyl group) from the calculation.

[0048] In other words, the above description defines the relationship between the molecular long axes determined by different pairs of substituents in each of the complexes represented by Formula I, Formula II, and Formula III. Each of the above-identified pairs of substituents defines the long axis of the molecule that is coordinated to the metal M 1 or M 2 The two endpoints of the long axis of each molecule are the atoms in each pair of substituents that are furthest away from the corresponding coordinating metal.

[0049] In some embodiments of the compounds, each substituent R, R′, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R7 When more than monosubstituted, the two substituents in may be joined or fused to form a ring.

[0050] In some embodiments of the compound, M 1 is Ir and M 2 is Pt.

[0051] In some embodiments of the compounds, ring A, ring B, ring C, ring D, ring E, and ring F are each independently selected from the group consisting of phenyl, pyridine, and imidazole. In some embodiments of the compounds, ring A, ring C, and ring E in Formula I and Formula III, and ring A and ring D in Formula II, are phenyl.

[0052] In some embodiments of the compounds, rings B, D, and F in formulas I and III, and rings B and C in formula II, are selected from the group consisting of pyridine, pyrimidine, imidazole, and pyrazole.

[0053] In some embodiments of the compounds, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, silyl, aryl, heteroaryl, and combinations thereof.

[0054] In some embodiments of the compound, the first distance is at least 4.3 Å longer than the second distance and the third distance, respectively, and the fourth distance is at least 4.3 Å longer than the fifth distance. The value of 4.3 Å is typical of the diameter of a phenyl ring. Thus, the first distance in the compound is at least one phenyl substitution longer than the second distance and the third distance, and the fourth distance is at least one phenyl substitution longer than the fifth distance.

[0055] In some embodiments of the compound, the first distance is at least 5.9 Å longer than the second distance and the third distance, and the fourth distance is at least 5.9 Å longer than the fifth distance, the value of 5.9 Å being representative of the distance spanning a para-tolyl group.

[0056] In some embodiments of the compounds, at least one of ring A, ring B, ring C, ring D, ring E, and ring F is fused to another 5- or 6-membered ring. The other 5- or 6-membered ring can be an aromatic ring or a non-aromatic ring. The aromatic ring can be a phenyl ring.

[0057] In some embodiments wherein the compound has Formula I, at least one of the following is true: (i), (ii), and (iii) (i) One R 1 is one R 2 Combine with; (ii) One R 3 is one R 4 combine with; and (iii) One R 5 is one R 6 Combine with In some embodiments in which the compound has Formula II, at least one of the following (i) and (ii) is true: (i) One R 1 is one R 2 combine with; and (ii) One R 3 is one R 4 Combine with

[0058] In some embodiments, the first distance is at least 3.0 Å longer than the second distance and the third distance, and the fourth distance is at least 3.0 Å longer than the fifth distance, where 3.0 Å is typical of the distance spanning two methyl groups.

[0059] Table 1 below shows the maximum linear length determined along the long axis of various substituents. This maximum linear length is defined as the distance between the two atoms furthest apart along the long axis of a particular substituent. The values ​​shown can be used to estimate the difference in length between the long axes of two molecules, as defined above, in relation to the structures of Formula I, Formula II, and Formula III, depending on the substituent that is the difference between the long axes of the two molecules being compared. For example, if the difference in length between the long axes of two molecules is the result of one molecule's long axis being longer than the other by an additional phenyl substituent, the fourth notation in Table 1 below indicates that the difference in length between the long axes of the two molecules is at least 4.3 Å (an additional C-C bond is required to form the link). Any two or more of the following fragments can be linked together, and the distance can be calculated simply by summing these numbers and the C-C single bond distance used to connect them. [Table 1]

[0060] In some embodiments of the compound, the bidentate ligands AB, CD, and EF are each independently selected from the group consisting of: [ka] [ka] In the formula, X 1 ~X 13 are each independently selected from the group consisting of carbon and nitrogen; X is selected from the group consisting of BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R'', SiR'R'', and GeR'R''; R' and R'' may be fused or joined to form a ring; R a , R b , R c , and R drepresents mono-substitution to the maximum number of substitutions possible, or represents no substitution; R', R'', R a , R b , R c , and R d are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R a , R b , R c , and R d Any two substituents in may be fused or linked to form a ring. In some embodiments of the compound, the bidentate ligands AB, CD, and EF are each independently selected from the group consisting of: [ka] [ka] [ka]

[0061] In some embodiments of the compound, n1 is 1 and n2 is 0. In some embodiments, n1 is 1 and n2 is 1. In some embodiments, n1 is 0 and n2 is 0.

[0062] In some embodiments of the compounds, Q 1 , Q 2 , Q 3 , and Q 4 and Q are each a direct bond. 1 , Q 2 , Q 3 , and Q 4One of the is oxygen, and Q 1 , Q 2 , Q 3 , and Q 4 The remaining three of Q are direct bonds. 1 , Q 2 , Q 3 , and Q 4 Two of them are oxygen, and Q 1 , Q 2 , Q 3 , and Q 4 The remaining two are direct bonds.

[0063] In some embodiments of the compound, Z 1 , Z 2 , Z 3 , Z 4 Two of them are carbon atoms, and Z 1 , Z 2 , Z 3 , Z 4 The remaining two are nitrogen atoms. 1 , Z 2 , Z 3 , Z 4 Three of them are carbon atoms, and Z 1 , Z 2 , Z 3 , Z 4 The remaining one of Z is a nitrogen atom. 1 , Z 2 , Z 3 , Z 4 Each of is a carbon atom.

[0064] Q 1 , Q 2 , Q 3 , and Q 4 and R are each a direct bond, the compound is in a cis configuration. In some embodiments, the compound has at least one Pt-carbene bond or Ir-carbene bond.

[0065] In some embodiments of the compound, the compound of Formula III is selected from the group consisting of: [ka] [ka]

[0066] In some embodiments of the compound, the compound is selected from the group consisting of: [ka] [ka] [ka] [ka] [ka] wherein X is selected from the group consisting of O, Se, and Se; X' is carbon or nitrogen; R 1’ , R 2’ , R 3’ , and R 4’ represents the maximum number of substitutions possible, from mono-substitution to no substitution, respectively; R 1’ , R 2’ , R 3’ , and R 4’ are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R, R', R 1 , R 2 , R 3 , R 4 , R5 , R 6 , and R 7 Any two substituents in may be bonded or fused to form a ring. In some embodiments of the compounds, at least one R 1 is para-positioned to the N coordinated to Ir, and at least one R 4 is para to the carbon coordinated to Ir. In some other embodiments of the compound, R 1 and R 1 At least one of ' and at least one R 4 and R 4 is selected from the group consisting of: [ka] [ka] [ka] [ka] [ka]

[0067] In some embodiments of the compound, the compound is selected from the group consisting of: [ka] [ka] [ka] [ka] [ka] [ka]

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[0068] According to another aspect of the present disclosure, an organic light-emitting device (OLED) is disclosed, the OLED comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising a compound represented by a formula selected from the group consisting of: [ka] wherein ring A, ring B, ring C, ring D, ring E, and ring F are each a 5- or 6-membered carbocyclic or heterocyclic ring; In Formula I: AB, CD, and EF are metals M 1 and forming three bidentate ligands coordinated with; AB, CD, and EF are different from one another; in the octahedral coordination configuration, ring A is trans to ring D, ring B is trans to ring E, and ring C is trans to ring F; In Formula II: AB, CD, and one acetylacetonate ligand are linked to a metal M 1 and form three bidentate ligands coordinated with; AB and CD are different from one another; in the octahedral coordination configuration, ring A is trans to ring D, ring B is trans to the oxygen atom, and ring C is trans to the oxygen atom; In Formula III: L 1 and L 3are each independently selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO, CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; n1 and n2 are each independently 0 or 1; when n1 or n2 is 1, L 2 or L 4 is selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO, CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; when n1 or n2 is 0, L 2 or L 4 does not exist;Q 1 , Q 2 , Q 3 , and Q 4 are each independently selected from the group consisting of a direct bond and oxygen; Z 1 , Z 2 , Z 3 , and Z 4 If any of the Qs is nitrogen, they will be bonded to 1 , Q 2 , Q 3 , and Q 4 is a direct bond; In a square planar configuration, ring A is trans to ring D and ring B is trans to ring C; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 represents the maximum number of substitutions possible, from mono-substitution to no substitution, respectively; Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , and Z 6 are each independently selected from the group consisting of carbon and nitrogen; M 1 is a metal selected from the group consisting of Ir, Os, Rh, Ru, and Re; M 2 is a metal selected from the group consisting of Pt and Pd; The first distance is R 1 M inside 1 The atom furthest away from R 4 M inside 1 is the distance between the atom furthest away from the The second distance is R 2 M inside 1 The atom furthest away from R 5 M inside 1 is the distance between the atom furthest away from the The third distance is R 3 M inside 1 The atom furthest away from R 6 M inside 1 is the distance between the atom furthest away from the The fourth distance is R 1 M inside 2 The atom furthest away from R 4 M inside 2 is the distance between the atom furthest away from the The fifth distance is R 2 M inside 2 The atom furthest away from R 3 M inside 2 is the distance between the atom furthest away from the the first distance is greater than the second distance and the third distance by at least 1.5 Å; the fourth distance is at least 1.5 Å greater than the fifth distance; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Any two substituents in may be bonded or fused to form a ring.

[0069] In some embodiments of the OLED in which the compound in the organic layer is according to Formula I, at least one of the following (i), (ii), and (iii) is true: (i) One R 1 is one R 2 Combine with; (ii) One R 3 is one R 4 combine with; and (iii) One R 5 is one R 6 Combine with In some embodiments in which the compound has Formula II, at least one of the following (i) and (ii) is true: (i) One R 1 is one R 2 combine with; and (ii) One R 3 is one R 4 Combine with

[0070] In some embodiments of the OLED, the organic layer is an emissive layer and the compound is an emissive dopant or a non-emissive dopant.

[0071] In some embodiments of the OLED, the organic layer further comprises a host, wherein the host comprises a triphenylene containing benzo-fused thiophene or a benzo-fused furan; Any substituent in the host may independently be C n H 2n+1 , O.C. n H 2n+1 , OAr1, N(C n H 2n+1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 , C≡CC n H 2n+1 , Ar1, Ar1-Ar2, and C n H 2n -Ar1 is a non-fused substituent selected from the group consisting of, or the host is unsubstituted; n is from 1 to 10; Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

[0072] In some embodiments of the OLED, the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

[0073] In some embodiments of the OLED, the organic layer further comprises a host, wherein the host is selected from the group consisting of: [ka] [ka]

[0074] In some embodiments of the OLED, the organic layer further comprises a host, and the host comprises a metal complex.

[0075] According to another aspect, a consumer product is disclosed that includes the OLED described above. In some embodiments of the consumer product, the consumer product is selected from the group consisting of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for indoor or outdoor illumination and / or signaling, a head-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a mobile phone, a tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay, a 3-D display, a virtual reality or augmented reality display, a car, a video wall including multiple displays aligned together, a theater or stadium screen, and a sign.

[0076] According to another aspect, a composition is disclosed that includes a compound having a formula selected from the group consisting of: [ka] wherein ring A, ring B, ring C, ring D, ring E, and ring F are each a 5- or 6-membered carbocyclic or heterocyclic ring; In Formula I: AB, CD, and EF are metals M 1 and forming three bidentate ligands coordinated with; AB, CD, and EF are different from one another; in the octahedral coordination configuration, ring A is trans to ring D, ring B is trans to ring E, and ring C is trans to ring F; In Formula II: AB, CD, and one acetylacetonate ligand are linked to a metal M 1and form three bidentate ligands coordinated with; AB and CD are different from one another; in the octahedral coordination configuration, ring A is trans to ring D, ring B is trans to the oxygen atom, and ring C is trans to the oxygen atom; In Formula III: L 1 and L 3 are each independently selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO, CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; n1 and n2 are each independently 0 or 1; when n1 or n2 is 1, L 2 or L 4 is selected from the group consisting of a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, SO, CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; when n1 or n2 is 0, L 2 or L 4 does not exist;Q 1 , Q 2 , Q 3 , and Q 4 are each independently selected from the group consisting of a direct bond and oxygen; Z 1 , Z 2 , Z 3 , and Z 4 If any of the Qs is nitrogen, they will be bonded to 1 , Q 2 , Q 3 , and Q 4 is a direct bond; In a square planar configuration, ring A is trans to ring D and ring B is trans to ring C; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 represents the maximum number of substitutions possible, from mono-substitution to no substitution, respectively; Z 1 , Z 2 , Z 3 , Z 4 , Z 5, and Z 6 are each independently selected from the group consisting of carbon and nitrogen; M 1 is a metal selected from the group consisting of Ir, Os, Rh, Ru, and Re; M 2 is a metal selected from the group consisting of Pt and Pd; The first distance is R 1 M inside 1 The atom furthest away from R 4 M inside 1 is the distance between the atom furthest away from the The second distance is R 2 M inside 1 The atom furthest away from R 5 M inside 1 is the distance between the atom furthest away from the The third distance is R 3 M inside 1 The atom furthest away from R 6 M inside 1 is the distance between the atom furthest away from the The fourth distance is R 1 M inside 2 The atom furthest away from R 4 M inside 2 is the distance between the atom furthest away from the The fifth distance is R 2 M inside 2 The atom furthest away from R 3 M inside 2 is the distance between the atom furthest away from the the first distance is greater than the second distance and the third distance by at least 1.5 Å; the fourth distance is at least 1.5 Å greater than the fifth distance; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Any two substituents in may be bonded or fused to form a ring.

[0077] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can generate emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF) (also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0078] The OLEDs disclosed herein can be incorporated into one or more of consumer products, electronic component modules, and lighting panels. The organic layer can be an emissive layer, and in some embodiments, the compound can be an emissive dopant, while in other embodiments, the compound can be a non-emissive dopant.

[0079] The composition can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, a hole transport material, and an electron transport layer material disclosed herein.

[0080] Example

[0081] Synthesis of compound 437

[0082] Process 1 [ka] CC-2 (2.3 g, 2.71 mmol) was dissolved in dry dichloromethane (400 ml). The mixture was degassed with N2 and cooled to 0 °C. 1-Bromopyrrolidine-2,5-dione (0.81 g, 2.71 mmol) was dissolved in DCM (300 mL) and added dropwise. After the addition, the temperature was gradually raised to room temperature and stirred for 12 h. Saturated NaHCO3 (20 mL) solution was added. The organic phase was separated and collected. The solvent was removed, and the residue was applied to Celite and purified on a silica gel column eluted with toluene / heptane 70 / 30 (v / v) to give product CC-2-Br (0.6 g, 24%).

[0083] Process 2 [ka] CC-2-Br (0.72 g, 0.775 mmol) was dissolved in a mixture of toluene (40 mL) and water (4 mL). The mixture was purged with N for 10 min. K3PO4 (0.411 g, 1.937 mmol), SPhos (0.095 g, 0.232 mmol), Pd2dba3 (0.043 g, 0.046 mmol), and phenylboronic acid (0.189 g, 1.55 mmol) were added. The mixture was heated at 110 °C under N2 for 12 h. After that, the reaction was cooled to room temperature, and the product was extracted with DCM. The organic phase was separated and collected. The solvent was removed, and the residue was applied to Celite and purified on a silica gel column eluted with toluene / heptane 70 / 30 (v / v). The product was purified by crystallization from toluene / MeOH to give compound 437 (0.7 g).

[0084] Synthesis of compound 438 [ka] CC-2-Br-2 (0.6 g, 0.646 mmol) was dissolved in a mixture of toluene (100 mL) and water (10 mL). The mixture was purged with N for 10 min. K3PO4 (0.343 g, 1.61 mmol), SPhos (0.080 g, 0.19 mmol), Pd2dba3 (0.035 g, 0.039 mmol), and [1,1-biphenyl]4-ylboronic acid (0.256 g, 1.29 mmol) were added. The mixture was heated at 110 °C under N2 for 12 h. The reaction was then cooled to room temperature, the product was extracted with DCM, and the organic phase was separated. The solvent was removed, and the residue was applied to Celite and purified on a silica gel column eluted with toluene / heptane 70 / 30 (v / v). The product was purified by crystallization from toluene / MeOH to give compound 438 (0.64 g).

[0085] Synthesis of compound 161

[0086] Process 1 [ka] CC-1 (2.04 g, 2.500 mmol) was dissolved in dry dichloromethane (400 ml). The mixture was degassed with N2 and cooled to 0 °C. 1-Bromopyrrolidine-2,5-dione (0.445 g, 2.500 mmol) was dissolved in DCM (200 mL) and added dropwise. After the addition, the temperature was gradually raised to room temperature and stirred for 16 h. Saturated NaHCO3 (20 mL) solution was added. The organic phase was separated and collected. The solvent was removed, and the residue was applied to Celite and purified on a column of silica gel eluted with 70 / 30 toluene / heptane to give the product CC-1-Br (0.6 g).

[0087] Process 2 [ka] CC-1-Br (1.16 g, 1.296 mmol) was dissolved in a mixture of toluene (120 mL) and water (12.00 mL). The mixture was purged with N for 10 minutes. K3PO4 (0.688 g, 3.24 mmol), Sphos (0.160 g, 0.389 mmol), Pd2dba3 (0.071 g, 0.078 mmol), and phenylboronic acid (0.316 g, 2.59 mmol) were added. The mixture was heated at 110 °C under N2 for 16 hours. After the reaction was complete, it was cooled to room temperature and the product was extracted with DCM. The organic phase was separated and collected. The solvent was removed, and the residue was applied to Celite and purified on a silica gel column eluted with 70 / 30 toluene / heptane. The product was purified by recrystallization from toluene / MeOH to give compound 161 (1.0 g).

[0088] Synthesis of Compound 401

[0089] Process 1 [ka] Under nitrogen, 2-chloro-5-methylpyridine (10.03 g, 79 mmol), (3-chloro-4-methylphenyl)boronic acid (13.4 g, 79 mmol), and potassium carbonate (21.74 g, 157 mmol) were dissolved in a mixture of DME (150 mL) and water (20 mL) to give a colorless suspension. Pd(PPh3)4 (0.909 g, 0.786 mmol) was added to the reaction mixture, which was then degassed and heated to 95 °C for 12 h. After cooling to room temperature, the organic layer was separated and evaporated. The residue was subjected to silica gel column chromatography eluting with heptane / THF 9 / 1 (v / v). Crystallization from heptane afforded 10 g of a white solid (58% yield).

[0090] Process 2 [ka] Under nitrogen, 2-(3-chloro-4-methylphenyl)-5-methylpyridine (10 g, 45.9 mmol), ((methyl-d3)sulfonyl)methane-d3 (92 g, 919 mmol), and sodium 2-methylpropan-2-olate (2.65 g, 27.6 mmol) were dissolved together to give a dark solution. The reaction mixture was heated to 80 °C under nitrogen for 12 h, cooled, diluted with ethyl acetate, washed with water, dried over sodium sulfate, filtered, and evaporated. Purification by silica gel column chromatography eluting with heptane / THF 9 / 1 (v / v) gave a white solid, which was subsequently crystallized from heptane to give a colorless crystalline material (9.1 g, 81% yield).

[0091] Process 3 [ka] Under nitrogen, 2-(3-chloro-4-(methyl-d3)phenyl)-5-(methyl-d3)pyridine (7.45 g, 33.3 mmol), phenylboronic acid (6.09 g, 49.9 mmol), potassium phosphate (15.34 g, 66.6 mmol), Pd2(dba)3 (0.305 g, 0.333 mmol), and dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphane (Sphos, 0.273 g, 0.666 mmol) were dissolved in a mixture of DME (150 mL) and water (25 mL) to give a red suspension. The reaction mixture was degassed under nitrogen and heated to reflux. After heating overnight, approximately 80% conversion was achieved. Further addition of boronic acid and catalyst did not improve the conversion. The organic phase was separated and evaporated, and the residue was purified by silica gel column chromatography eluted with heptane / THF 9 / 1, followed by crystallization from heptane: white solid (6.2 g, 70% yield).

[0092] Process 4 [ka] Under a nitrogen atmosphere, 4,5-bis(methyl-d3)-2-phenylpyridine (1.427 g, 7.54 mmol), 5-(methyl-d3)-2-(6-(methyl-d3)-[1,1'-biphenyl]-3-yl)pyridine (2 g, 7.54 mmol), and [IrCl(COD)]2 (2.53 g, 3.77 mmol) were dissolved in ethoxyethanol (50 mL) under nitrogen to give a red solution. The reaction mixture was heated to reflux for 1 h, after which a precipitate formed. 30 mL more of ethoxyethanol was added, and refluxing was continued for 48 h, after which the reaction mixture was cooled to room temperature. The crude material was used in the next step without further purification.

[0093] Process 5 [ka] Under a nitrogen atmosphere, the iridium dimer (from step 4) suspended in ethoxyethanol was mixed with pentane-2,4-dione (2.59 g, 25.9 mmol) and sodium carbonate (3.43 g, 32.3 mmol) in 50 ml of methanol, stirred at 55° C. under nitrogen for 24 hours, and evaporated. The yellow residue was subjected to silica gel column chromatography eluting with a gradient mixture of heptane / toluene to give 5 g of the desired acac complex (36% yield).

[0094] Process 6 [ka] The acac complex (5 g, 6.72 mmol) was dissolved in DCM (20 mL), then HCl in ether (16.80 mL, 33.6 mmol) was added in one portion, stirred for 10 minutes, and evaporated. The residue was triturated with methanol. The solid was filtered and washed with methanol and heptane to give a yellow solid (4.55 g, 100% yield).

[0095] Process 7 [ka] Ir dimer (4.55 g, 3.34 mmol) and (((trifluoromethyl)sulfonyl)oxy)silver (2.062 g, 8.03 mmol) were suspended in 50 ml of a 1 / 1 (v / v) mixture of DCM / methanol, stirred at room temperature for 72 h, filtered through Celite, and evaporated to give a yellow solid (4.75 g, 83% yield).

[0096] Process 8 [ka] A mixture of triflate (3 g, 3.5 mmol) and 2-(13-methyl-d2)-8-(4-(2,2-dimethylpropyl-1,1-d2)pyridin-2-yl)benzofuro[2,3-b]pyridine (2.56 g, 7.7 mmol) in 30 mL of methanol was stirred under nitrogen at 65 °C for 5 days. The material was then cooled and the methanol was evaporated. The residue was subjected to silica gel column chromatography eluting with 2% ethyl acetate in toluene to give two isomers of the product (higher R f 1.7 g of complex with low R f (0.7 g of complex with low R f The complex having the formula: is the target compound 401.

[0097] Device Example

[0098] All of the example devices were fabricated under high vacuum (<10 -7The devices were fabricated by thermal evaporation at 1000 Torr. The anode electrode was 750 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of Liq (8-hydroxyquinoline lithium) and 1,000 Å of Al. All devices were immediately encapsulated with a glass lid sealed with epoxy resin in a nitrogen glove box (H2O and O2 <1 ppm) after fabrication, and a moisture getter was included in the package. The organic stack of the device example consisted of, from the ITO surface, 100 Å of HAT-CN as a hole-injection layer (HIL); 450 Å of HTM as a hole-transport layer (HTL); and a 400 Å-thick light-emitting layer (EML). The light-emitting layer contained a 6:4 ratio of H-host (H1):E-host (H2) and 12 wt% of a green emitter. As ETL, 350 Å of Liq (8-hydroxyquinoline lithium) was doped with 40% ETM. The device structure is shown in Table 1. Table 1 shows a schematic device structure. The chemical structures of the device materials are shown below. [ka] [ka]

[0099] For the fabricated device, DC 80mA / cm 2 The EL, JVL, and lifetime were measured. The device performance is shown in Table 3. The voltage, LE, EQE, PE, and LT 97% In all cases, the comparative compound was used as the standard. [Table 2] Schematic device structure [Table 3] Device performance

[0100] Comparing Compound 437 and Compound 438 with the Comparative Example, the efficiency of both Compound 437 and Compound 438 is higher than that of the Comparative Example. Presumably, Compound 437 and Compound 438 have a higher horizontal emitting dipole orientation than the Comparative Example. The extended planar substituents with high electrostatic potential increase the surface area for interaction between the Ir complex and the host molecule, thereby stacking the Ir complex parallel to the film surface and increasing the outcoupling efficiency. Furthermore, both Compound 437 and Compound 438 exhibited a luminous flux of 80 mA / cm. 2 LT in 97% is superior to that of the comparative example, suggesting that the extended substituent not only increases the efficiency but also the stability of the complex in the device.

[0101] A summary of device data recorded at 9000 nits for the device examples is provided below in Table 4. EQE values ​​are based on device C-2. [Table 4] The data in Table 4 show that devices using the inventive compounds as emitters achieved higher efficiencies than the comparative example, despite the same color. Notably, the only difference between the inventive and comparative compounds (CC-1) is that the inventive compounds have a phenyl moiety replacing one of the protons in the comparative compound, thereby increasing the distance between the terminal atoms in one direction across the Ir metal center. The device results indicate that a larger aspect ratio of the emitter molecules appears to be important in achieving higher device efficiencies. Combination with other materials

[0102] The materials described herein as useful for a particular layer in an organic light-emitting device can be used in combination with a wide variety of other materials present in the device. For example, the emissive dopants disclosed herein can 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 referenced below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that may be useful in combination.

[0103] Conductive dopants: The charge transport layer is doped with a conductive dopant to significantly change the density of charge carriers and thereby its conductivity. The conductivity can be increased by generating charge carriers in the matrix material or, depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductive dopant, and n-type conductive dopants are used in the electron transport layer.

[0104] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are illustrated below, along with references that disclose these materials. EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO 06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US2012146012 [ka] HIL / HTL:

[0105] The hole injection / transport material used in the embodiments of the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injection / transport material. Examples of such materials include phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorocarbons; polymers with conductive dopants; conductive polymers such as PEDOT / PSS; self-assembly monomers derived from compounds such as phosphonic acid and silane derivatives; MoO x p-type semiconducting organic compounds such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile; metal complexes, and crosslinkable compounds.

[0106] Examples of aromatic amine derivatives used in the HIL or HTL include, but are not limited to, the following general structures: [ka]

[0107] Ar 1 From Ar 9are a group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; 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, indole, and aromatic heterocyclic compounds such as oxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and 2 to 10 cyclic structural units of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, which are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic cyclic group. Each Ar can be unsubstituted or substituted with 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 acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0108] In one embodiment, Ar 1 From Ar9 teeth, [ka] are independently selected from the group consisting of: where k is an integer from 1 to 20; X 101 From X 108 is C (including CH) or N; Z 101 is NAr 1 , O, or S; Ar 1 has the same radical as defined above.

[0109] Examples of metal complexes used in the HIL or HTL include, but are not limited to, those of the following general formula: [ka] where Met is a metal that may have an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, and 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 can be attached to the metal; and k'+k'' is the maximum number of ligands that can be attached to the metal.

[0110] In one embodiment, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. 101 -Y 102 ) is a carbene ligand. In another embodiment, Met is selected from Ir, Pt, Os, and Zn. In a further embodiment, the metal complex is + For the / Fc couple, it has a minimum oxidation potential of less than about 0.6 V in solution.

[0111] Non-limiting examples of HIL and HTL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references that disclose these 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 [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0112] An electron blocking layer (EBL) can 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 can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. Blocking layers can also 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 a 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 a higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as one of the hosts described below. host:

[0113] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as a light-emitting material, and may also contain a host material that uses the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is higher than that of the dopant. Any host material may be used with any dopant as long as the triplet criterion is met.

[0114] Examples of metal complexes used as host materials preferably have the following general formula: [ka] where Met is a metal; 103 -Y 104 ) is a bidentate ligand, and Y 103 and Y 104 are independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k'' is the maximum number of ligands that can be attached to the metal.

[0115] In one embodiment, the metal complex is: [ka] where (ON) is a bidentate ligand with the metal coordinated to atoms O and N.

[0116] In another embodiment, Met is selected from Ir and Pt. 103 -Y 104 ) is a carbene ligand.

[0117] Examples of other organic compounds used as the host material include aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, and benzimidazoline. and aromatic heterocyclic compounds such as benzofuropyridine, 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 aromatic hydrocarbon ring groups and aromatic heterocyclic groups, which may be the same or different groups and which are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic cyclic group. Each option in each group can be unsubstituted or substituted with 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 acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0118] In one embodiment, the host compound contains at least one of the following groups in the molecule: [ka] In the formula, R 101 From R 107 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, has the same definition as Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20; and k''' is an integer from 0 to 20. X 101 From X 108 is selected from C (including CH) or N. Z 101 and Z 102 is NR 101 , O, or S.

[0119] Non-limiting examples of host materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references that disclose these materials. EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR201301 15564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090 167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US201 2075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US201402 25088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO20 09066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO201212 8298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472

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[0120] One or more additional emitter dopants can be used together with the compound of the present disclosure.The example of the additional emitter dopant is not particularly limited, and any compound can be used as long as the compound is typically used as an emitter material.Suitable emitter materials include, but are not limited to, compounds that can generate light emission through phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0121] Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references that disclose these 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, US 2014103305, US6303238, US6413656, US6653654, US6670645, US6687266, US6835469, US6921915, US7279704, US73 32232, US7378162, US7534505, US7675228, US7728137, US7740957, US7759489, US7951947, US8067099, US8592586 , US8871361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO200201 5645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842 , WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO20 11044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO201317 4471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450,

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[0122] A hole-blocking layer (HBL) can be used to reduce the number of holes and / or excitons that escape from the emissive layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also 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 a 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 a higher triplet energy than one or more of the hosts closest to the HBL interface.

[0123] In one embodiment, the compound used in the HBL comprises the same molecule as that used as the host described above.

[0124] In another embodiment, the compound used in the HBL contains at least one of the following groups in the molecule: [ka] where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3. ETL:

[0125] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound typically used to transport electrons may be used.

[0126] In one embodiment, the compound used in the ETL contains at least one of the following groups in the molecule: [ka] In the formula, 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 acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, has the same definition as that of Ar mentioned above. 1 From Ar 3 has the same definition as that of Ar mentioned above. k is an integer from 1 to 20. X 101 From X 108 is selected from C (including CH) or N.

[0127] In another embodiment, the metal complex used in the ETL comprises, but is not limited to, the following general formula: [ka] where (ON) or (NN) is a bidentate ligand with the metal coordinated to atoms O, N or N, N; 101 is another ligand; and k' is an integer value between 1 and the maximum number of ligands that can be attached to the metal.

[0128] Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references that disclose these materials. CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2 005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, U S20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US20 11210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO2007111263, WO20 09148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO 2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535. [ka] [ka] [ka] Charge generation layer (CGL)

[0129] In tandem or stacked OLEDs, the CGL plays a key role in performance and consists of an n-doped layer and a p-doped layer for electron and hole injection, respectively. Electrons and holes are supplied from the CGL and the electrodes. Consumed electrons and holes in the CGL are replenished by electrons and holes injected from the cathode and anode, respectively, until the bipolar current gradually reaches a steady state. Typical CGL materials contain n-type and p-type conductivity dopants used in the transport layers.

[0130] In any of the above-mentioned compounds used in each layer of an OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any specifically mentioned substituent, such as, but not limited to, methyl, phenyl, pyridyl, etc., can be their undeuterated, partially deuterated, and fully deuterated versions. Similarly, substituent classes, such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc., can be their undeuterated, partially deuterated, and fully deuterated versions.

[0131] 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 can be substituted with other materials and structures without departing from the spirit of the invention. Thus, the present invention as claimed may include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It is understood that various theories as to why the invention works are not intended to be limiting. [Prior art documents] [Patent documents]

[0132] [Patent Document 1] U.S. Patent No. 5,844,363 [Patent Document 2] U.S. Patent No. 6,303,238 [Patent Document 3] U.S. Patent No. 5,707,745 [Patent Document 4] U.S. Patent No. 7,279,704 [Explanation of symbols]

[0133] 100 Organic Light-Emitting Devices 110 Substrate 115 Anode 120 Hole injection layer 125 Hole transport layer 130 Electron Blocking Layer 135 Light-emitting layer 140 Hole Blocking Layer 145 Electron transport layer 150 Electron injection layer 155 Protective layer 160 cathode 162 First conductive layer 164 Second Conductive Layer 170 Barrier Layer 200 Inverted OLED, device 210 Substrate 215 cathode 220 Light-emitting layer 225 Hole transport layer 230 Anode

Claims

1. A compound represented by a formula selected from the group consisting of: 【Chemistry 1】 wherein ring A, ring B, ring C, ring D, ring E, and ring F are each a 5- or 6-membered carbocyclic or heterocyclic ring; In Formula III: L １ and L ３ are each independently a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, or SO ２ , CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; n １ , n ２ are each independently 0 or 1, n １ or n ２ If is 1, L ２ or L ４ is a direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO ２ , CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; n １ or n ２ If is 0, L ２ or L ４ does not exist; Q １ , Q ２ , Q ３ , and Q ４ are each independently selected from the group consisting of a direct bond and oxygen; Z １ , Z ２ , Z ３ , and Z ４ If any of the Q １ , Q ２ , Q ３ , and Q ４ is a direct bond, In the square planar configuration, ring A is trans to ring D and ring B is trans to ring C; In Formula I: AB, CD, and EF are metals M １ to form three bidentate ligands coordinated with A-B, C-D, and E-F are different from one another; In the octahedral coordination configuration, ring A is in the trans position relative to ring D, ring B is in the trans position relative to ring E, and ring C is in the trans position relative to ring F; R １ , R ２ , R ３ , R ４ , R ５ , and R ６ represents mono-substitution to the maximum possible number of substitutions, or represents no substitution, respectively; Z １ , Z ２ , Z ３ , Z ４ , Z ５ , and Z ６ are each independently selected from the group consisting of carbon and nitrogen; M １ is a metal selected from the group consisting of Ir, Os, Rh, Ru, and Re; M ２ is a metal selected from the group consisting of Pt and Pd; The first distance is M １ The R that is the furthest away from １ Atoms in and M １ The R that is the furthest away from ４ is the distance between the atoms in The second distance is M １ The R that is the furthest away from ２ Atoms in and M １ The R that is the furthest away from ５ is the distance between the atoms in The third distance is M １ The R that is the furthest away from ３ Atoms in and M １ The R that is the furthest away from ６ is the distance between the atoms in The fourth distance is M ２ The R that is the furthest away from １ Atoms in and M ２ The R that is the furthest away from ４ is the distance between the atoms in The fifth distance is M ２ The R that is the furthest away from ２ Atoms in and M ２ The R that is the furthest away from ３ is the distance between the atoms in the first distance is at least 1.5 Å longer than the second distance and the third distance, respectively; the fourth distance is at least 1.5 Å greater than the fifth distance; R, R', R １ , R ２ , R ３ , R ４ , R ５ , and R ６ are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R, R', R １ , R ２ , R ３ , R ４ , R ５ , and R ６ Any two substituents in may be bonded or fused to form a ring.

2. The compound of claim 1 , wherein rings A, C, and E in formula I and formula III are phenyl.

3. The compound of claim 1 , wherein rings B, D, and F in formula I and formula III are selected from the group consisting of pyridine, pyrimidine, imidazole, and pyrazole.

4. R １ , R ２ , R ３ , R ４ , R ５ , and R ６ 10. The compound of claim 1, wherein each is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, silyl, aryl, heteroaryl, and combinations thereof.

5. 2. The compound of claim 1, wherein at least one of ring A, ring B, ring C, ring D, ring E, and ring F is fused with another 5- or 6-membered ring.

6. In Formula I: (i) One R １ is one R ２ Combine with; (ii) one R ３ is one R ４ combines with; and (iii) one R ５ is one R ６ Combine with The compound of claim 1, wherein at least one of the following applies:

7. 2. The compound of claim 1, wherein the bidentate ligands AB, CD, and EF are each independently selected from the group consisting of: 【Chemistry 2】 【Transformation 3】 (In the formula, X １ ~X １３ are each independently selected from the group consisting of carbon and nitrogen; X is BR', NR', PR', O, S, Se, C=O, S=O, SO ２ , CR′R″, SiR′R″, and GeR′R″; R′ and R″ may be fused or joined to form a ring; Ra, Rb, Rc, and Rd each represent mono-substitution to the maximum possible number of substitutions, or represent no substitution; R', R'', Ra, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; Any two substituents in Ra, Rb, Rc, and Rd may be fused or bonded to form a ring.

8. 2. The compound of claim 1, wherein the compound of formula III is selected from the group consisting of: 【Chemistry 4】 【Transformation 5】

9. 2. The compound of claim 1, wherein the compound is selected from the group consisting of: 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 wherein X is selected from the group consisting of O and Se; X' is carbon or nitrogen; R １ ', R ２ ', R ３ ', and R ７ represents mono-substitution to the maximum possible number of substitutions, or represents no substitution, respectively; R １ ', R ２ ', R ３ ', and R ７ are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R １ ', R ２ ', R ３ ', and R ７ Any two substituents in may be bonded or fused to form a ring.

10. At least one R １ is in the para position relative to the N coordinated to Ir, and at least one R ４ is para to the carbon coordinated to Ir; or R １ and R １ ' and at least one of R ４ and R ４ 10. The compound of claim 9, wherein at least one of is selected from the group consisting of: 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】

11. 2. The compound of claim 1, wherein the compound is selected from the group consisting of: 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【Chemistry 27】 【Chemistry 28】 【Chemistry 29】 【Transformation 30】 【Chemistry 31】 【Chemistry 32】 【Transformation 33】 【Transformation 34】 【Chemistry 35】 【Transformation 36】 【Chemistry 37】 【Transformation 38】 【Chemistry 39】 【Chemistry 40】 【Chemistry 41】 【Chemistry 42】 【Chemistry 43】 【Chemistry 44】 【Chemistry 45】 【Chemistry 46】 【Chemistry 47】 【Chemistry 48】 【Chemistry 49】 [Transformation 50] 【Chemistry 51】 【Chemistry 52】 【Chemistry 53】 【Chemistry 54】 【Transformation 55】 【Transformation 56】 【Chemistry 57】 【Chemistry 58】 【Chemistry 59】

12. an anode; a cathode; an organic layer disposed between the anode and the cathode, the organic layer comprising a compound represented by a formula selected from the group consisting of: 【Transformation 60】 wherein ring A, ring B, ring C, ring D, ring E, and ring F are each a 5- or 6-membered carbocyclic or heterocyclic ring; In Formula III: L １ and L ３ are each independently a direct bond, BR, NR, PR, O, S, Se, C═O, S═O, or SO ２ , CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; n １ , n ２ are each independently 0 or 1, n １ or n ２ If is 1, L ２ or L ４ is a direct bond, BR, NR, PR, O, S, Se, C=O, S=O, SO ２ , CRR′, SiRR′, GeRR′, alkyl, and combinations thereof; n １ or n ２ If is 0, L ２ or L ４ does not exist; Q １ , Q ２ , Q ３ , and Q ４ are each independently selected from the group consisting of a direct bond and oxygen; Z １ , Z ２ , Z ３ , and Z ４ If any of the Q １ , Q ２ , Q ３ , and Q ４ is a direct bond, In the square planar configuration, ring A is trans to ring D and ring B is trans to ring C; In Formula I: AB, CD, and EF are metals M １ to form three bidentate ligands coordinated with A-B, C-D, and E-F are different from one another; In the octahedral coordination configuration, ring A is in the trans position relative to ring D, ring B is in the trans position relative to ring E, and ring C is in the trans position relative to ring F; R １ , R ２ , R ３ , R ４ , R ５ , and R ６ represents mono-substitution to the maximum possible number of substitutions, or represents no substitution, respectively; Z １ , Z ２ , Z ３ , Z ４ , Z ５ , and Z ６ are each independently selected from the group consisting of carbon and nitrogen; M １ is a metal selected from the group consisting of Ir, Os, Rh, Ru, and Re; M ２ is a metal selected from the group consisting of Pt and Pd; The first distance is M １ The R that is the furthest away from １ Atoms in and M １ The R that is the furthest away from ４ is the distance between the atoms in The second distance is M １ The R that is the furthest away from ２ Atoms in and M １ The R that is the furthest away from ５ is the distance between the atoms in The third distance is M １ The R that is the furthest away from ３ Atoms in and M １ The R that is the furthest away from ６ is the distance between the atoms in The fourth distance is M ２ The R that is the furthest away from １ Atoms in and M ２ The R that is the furthest away from ４ is the distance between the atoms in The fifth distance is M ２ The R that is the furthest away from ２ Atoms in and M ２ The R that is the furthest away from ３ is the distance between the atoms in the first distance is at least 1.5 Å longer than the second distance and the third distance, respectively; the fourth distance is at least 1.5 Å greater than the fifth distance; R, R', R １ , R ２ , R ３ , R ４ , R ５ , and R ６ are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R, R', R １ , R ２ , R ３ , R ４ , R ５ , and R ６ Any two substituents in may be bonded or fused to form a ring.

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