Organic electroluminescent materials and devices

Abstract

To provide a new substance composition for a host material in an OLED.SOLUTION: The inclusion of deuterated moieties in organic molecules provides new compositions of matter for host materials in OLEDs. Compositions comprising these deuterated compounds are also provided. Further provided are OLEDs and related consumer products that utilize these deuterated compounds. Wherein at least one of RAL and RAM and at least one of RAN is D. ) SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application Nos. 63 / 229,748, filed August 5, 2021, 63 / 220,429, filed July 9, 2021, and 63 / 154,320, filed February 26, 2021, the disclosures of which are incorporated herein by reference in their entireties. This application is a continuation-in-part of co-pending U.S. patent application Ser. No. 17 / 063,884, filed October 6, 2020, which also claims priority to U.S. Provisional Application Nos. 62 / 982,883, filed February 28, 2020, 62 / 971,295, filed February 7, 2020, and 62 / 926,035, filed October 25, 2019, the disclosures of which are incorporated herein by reference in their entireties.

[0002] FIELD OF THE DISCLOSURE This disclosure relates generally to organometallic compounds and compositions and their various uses, including as hosts or emitters in devices such as organic light emitting diodes and related electronic devices. [Background technology]

[0003] Optoelectronic devices that utilize organic materials are becoming increasingly desirable for a variety of 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 certain 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.

[0004] OLEDs utilize thin organic films that emit light when a voltage is applied across the device, and are becoming an increasingly interesting technology for use in applications such as flat panel displays, lighting, and backlighting.

[0005] One application of phosphorescent 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 absorption filters to produce red, green, and blue emission. Similar techniques can be used with OLEDs. White OLEDs can be either single-emissive-layer (EML) devices or stacked structures. Color can be measured using CIE coordinates, which are well known in the art. Summary of the Invention

[0006] In one aspect, the present disclosure provides a compound selected from the group consisting of formulas (1) to (16) shown below. [ka] (In the formula, R A and at least one of R B At least one of is D.) [ka] (In the formula, R C and R D At least one of is D.) [ka] (In the formula, R E , R F , R G , and R H At least one of is D.) [ka] (In the formula, R I , R J , and R K At least one of is D.) [ka] (In the formula, R L , R M , and R N At least one of is D.) [ka] (In the formula, R O , R P , and R Q At least one of is D.) [ka] (In the formula, R R and R S At least one of is D.) [ka] (In the formula, R T , R U , R V , and R W At least one of is D.) [ka] (In the formula, R X and R Y At least one of them is D.) [ka] (In the formula, R AB and R AC At least one of them is D.) [ka] (In the formula, R AF and R AG At least one of is D.) [ka] (In the formula, R AL and R AM At least one of and R AN At least one of is D.) [ka] (In the formula, R AT , R AU , R AV , and R AW At least one of is D.) [ka] (In the formula, R AY and R AZ at least one of is D); During the ceremony: R A ~R BB each independently represent the maximum number of substitutions possible from mono to no substitution; X 1 ~X 138 are each independently C or N; X 1 ~X 8 At least one of and 114 ~X 116 One of them is N; X 32 and X 34 at least one of is C; Y 1 ~Y 5 are each independently selected from the group consisting of O, S, and Se; Y 2 and Y 3 One of the may represent no bond; L is a direct bond or an organic linker; R E , R F , R G , and R Hat least one of is selected from the group consisting of aryl, heteroaryl, amino, silyl, boryl, and combinations thereof; R A ~R S , R AL ~R AO , R AY , R AZ , R BA , and R BB any two adjacent substituents of may be joined or fused to form a ring; However, R L , R M , and R N any two adjacent substituents are not joined or fused to form an indolo[3,2,1-jk]carbazole; Each R Y is H or D; R 2 and R 3 at least one of comprises a chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and a boron atom; R 8 is selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof; R A ~R AO , R AT ~R BB , R 1 ~R 7are each independently a substituent selected from the group consisting of hydrogen or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; When the compound has the structure of formula (14), at least one of the following two conditions is met: (a)R AP ~R AS are each independently selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof; R AP ~R AS at least one of is unique; only said compound contains one Si; and (b)R AP ~R AS are each independently a substituent selected from the group consisting of hydrogen or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; R AP At least one of R AQ At least one of R AR and at least one of R ASat least one of is deuterium; Any adjacent R AP ~R AS can be joined or fused to form a ring; R AP ~R AS at least one of R comprises a group selected from the group consisting of triazine, pyrimidine, pyridine, pyrazine, boryl, silane, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, tetraphenylene, biscarbazole, and combinations thereof; AP ~R AS each does not contain a six-membered ring containing exactly one B and exactly one N; However, the compound is not one of the following: [ka]

[0007] In another aspect, the present disclosure provides a composition comprising a compound selected from the group consisting of Formulas (1) to (14) described herein.

[0008] In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound selected from the group consisting of Formulas (1) to (14) described herein.

[0009] In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a compound selected from the group consisting of Formulas (1) through (14) described herein. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 shows an organic light-emitting device.

[0011] [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

[0012] A. Terminology Unless otherwise stated, the following terms used herein are defined as follows:

[0013] 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 all dendrimers currently used in the field of OLEDs are considered to be small molecules.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] As used herein, and as generally understood by those skilled in the art, a first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. 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.

[0018] As used herein, and as generally 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.

[0019] The terms "halo," "halogen," and "halide" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0020] The term "acyl" refers to a substituted carbonyl group (C(O)-R s ) refers to

[0021] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s or -C(O)-OR s ) group.

[0022] The term "ether" means -OR s Refers to the base.

[0023] The terms "sulfanyl" and "thioether" are used interchangeably, and -SR s Refers to the base.

[0024] The term "selenyl" refers to SeR s Refers to the base.

[0025] The term "selenyl" refers to SeR s Refers to the base.

[0026] The term "sulfinyl" refers to -S(O)-R s Refers to the base.

[0027] The term "sulfonyl" means -SO2-R s Refers to the base.

[0028] The term "phosphino" refers to -P(R s ) refers to three groups, each R s may be the same or different.

[0029] The term "silyl" refers to -Si(R s ) refers to three groups, each R s may be the same or different.

[0030] The term "germyl" refers to -Ge(R s ) refers to three groups, each R s may be the same or different.

[0031] The term "germyl" refers to -Ge(R s ) refers to three groups, each R s may be the same or different.

[0032] The term "boryl" means -B(R s ) group or its Lewis adduct -B(R s ) 3 groups, R s may be the same or different.

[0033] In each of the above, R s can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0034] The term "alkyl" refers to and includes both straight-chain and branched-chain alkyl groups. Preferred alkyl groups contain from 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. Additionally, the alkyl groups may be optionally substituted.

[0035] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups contain 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Furthermore, the cycloalkyl groups may be optionally substituted.

[0036] The terms "heteroalkyl" or "heterocycloalkyl" refer to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Furthermore, the heteroalkyl or heterocycloalkyl group may be optionally substituted.

[0037] The term "alkenyl" refers to and includes both straight-chain and branched-chain alkene groups. An alkenyl group is essentially an alkyl group containing at least one carbon-carbon double bond in the alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group containing at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group having at least one carbon atom replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkenyl, cycloalkenyl, or heteroalkenyl group may be optionally substituted.

[0038] The term "alkynyl" refers to and includes both straight-chain and branched-chain alkyne groups. Alkynyl groups are essentially alkyl groups containing at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. Furthermore, the alkynyl groups may be optionally substituted.

[0039] The terms "aralkyl" and "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group. In addition, said aralkyl group may be optionally substituted.

[0040] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Heteroaromatic cyclic groups may be used interchangeably with heteroaryl. Preferred heteroaromatic cyclic groups contain 3 to 7 ring atoms and include at least one heteroatom, including cyclic amines such as morpholino, piperidino, and pyrrolidino, and cyclic ethers / thioethers such as tetrahydrofuran, tetrahydropyran, and tetrahydrothiophene. Furthermore, the heterocyclic groups may be optionally substituted.

[0041] The term "aryl" refers to and includes both monocyclic aromatic hydrocarbyl groups and polycyclic aromatic ring systems. A polycyclic ring can have two or more rings in which two carbon atoms are shared between two adjacent rings (the rings are "fused"), at least one of which is an aromatic hydrocarbyl group, and the other rings can be, for example, a 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 carbons, 10 carbons, or 12 carbons are particularly preferred. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, and are preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Furthermore, the aryl group may be optionally substituted.

[0042] The term "heteroaryl" refers to and includes both monocyclic aromatic groups and polycyclic aromatic ring systems containing at least one heteroatom. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many instances, O, S, or N are preferred heteroatoms. Heteromonocyclic aromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the rings can have 1 to 6 heteroatoms. Heteropolycyclic ring systems can have two or more rings in which two atoms are common to two adjacent rings (the rings are "fused"), and at least one of the rings is heteroaryl; for example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Heteropolycyclic aromatic ring systems can have 1 to 6 heteroatoms per ring of the polycyclic aromatic ring system. 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.

[0043] Of the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole groups, and their respective aza analogues, are of particular interest.

[0044] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl are independently unsubstituted or independently substituted with one or more common substituents.

[0045] In many instances, the typical substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0046] In some instances, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.

[0047] In some instances, more preferred common substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boryl, aryl, heteroaryl, sulfanyl, and combinations thereof.

[0048] In still other instances, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0049] The terms "substituted" and "substituted" refer to a substituent other than H attached to the relevant position (e.g., carbon or nitrogen). For example, R 1 If represents a mono-substitution, one R 1 must be other than H (i.e., a substitution). Similarly, R 1 If represents a di-substitution, R 1 must be other than H. Similarly, R 1 When represents zero or no substitution, R1 can be a hydrogen at an available valence of a ring atom, as in the case of a carbon atom in benzene and a nitrogen atom in pyrrole, or simply represent nothing in the case of a ring atom with a fully satisfied valence (e.g., nitrogen in pyridine). The maximum number of substitutions possible in a ring structure depends on the total number of available valences on the ring atoms.

[0050] As used herein, "combinations thereof" refers to one or more members of the applicable list being combined to form known or chemically stable configurations that one skilled in the art can contemplate from the applicable list. For example, alkyl and deuterium can be combined to form a partially or fully deuterated alkyl group; halogen and alkyl can be combined to form a halogenated alkyl substituent; halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one example, the term "substituted" includes combinations of 2 to 4 of the listed groups. In another example, the term "substituted" includes combinations of 2 to 3 groups. In yet another example, the term "substituted" includes combinations of 2 groups. Preferred combinations of substituents are those containing up to 50 atoms that are not hydrogen or deuterium, or those containing up to 40 atoms that are not hydrogen or deuterium, or those containing up to 30 atoms that are not hydrogen or deuterium. In many examples, preferred combinations of substituents include up to 20 atoms that are not hydrogen or deuterium.

[0051] The designation "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 aromatic ring can be replaced by 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 readily envision other nitrogen analogs of the above-described aza derivatives, and all such analogs are intended to be encompassed by the terms described herein.

[0052] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, International Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. 2011 / 0037057, the entire contents of which are incorporated by reference, describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Tetrahedron 2015, 71, 1425-30 (Ming Yan et al.) and Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65 (Atzrodt et al.), the entire contents of which are incorporated by reference, which describe efficient routes for deuteration of methylene hydrogens in benzylamines and substitution of aromatic ring hydrogens with deuterium, respectively.

[0053] It is understood that when a molecular fragment is described as being a substituent or as being attached to another moiety, the name may be described as being the fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (e.g., benzene, naphthalene, dibenzofuran). Different designations of substituents or attached fragments are considered equivalent herein.

[0054] In some instances, adjacent pairs of substituents can be optionally bonded or fused to form a ring. Preferred rings are 5-, 6-, or 7-membered carbocyclic or heterocyclic rings, including both cases where the portion of the ring formed by the pair of substituents is saturated and cases where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that the two related substituents can be adjacent to each other on the same ring, or can be adjacent to each other on two rings with the two nearest available substitutable positions, such as the 2- and 2'-positions in biphenyl and the 1- and 8-positions in naphthalene, as long as a stable fused ring system can be formed.

[0055] B. Compounds of the Present Disclosure In one aspect, the present disclosure provides a compound selected from the group consisting of formulas (1) to (16) shown below. [ka] (In the formula, R A and at least one of R B At least one of is D.) [ka] (In the formula, R C and R D At least one of is D.) [ka] (In the formula, R E , R F , R G , and R H At least one of is D.) [ka] (In the formula, R I , R J , and R K At least one of is D.) [ka] (In the formula, R L , R M , and R N At least one of is D.) [ka] (In the formula, R O , R P , and R Q At least one of is D.) [ka] (In the formula, R R and R SAt least one of is D.) [ka] (In the formula, R T , R U , R V , and R W At least one of is D.) [ka] (In the formula, R X and R Y At least one of them is D.) [ka] (In the formula, R AB and R AC At least one of them is D.) [ka] (In the formula, R AF and R AG At least one of is D.) [ka] (In the formula, R AL and R AM At least one of and R AN At least one of is D.) [ka] (In the formula, R AT , R AU , R AV , and R AW At least one of is D.) [ka] (In the formula, R AY and R AZ at least one of is D); During the ceremony: R A ~R BBeach independently represent the maximum number of substitutions possible from mono to no substitution; X 1 ~X 138 are each independently C or N; X 1 ~X 8 At least one of and 114 ~X 116 One of them is N; X 32 and X 34 at least one of is C; Y 1 ~Y 5 are each independently selected from the group consisting of O, S, and Se; Y 2 and Y 3 One of the may represent no bond; L is a direct bond or an organic linker; R E , R F , R G , and R H at least one of is selected from the group consisting of aryl, heteroaryl, amino, silyl, boryl, and combinations thereof; R A ~R S , R AL ~R AO , R AY , R AZ , R BA , and R BB any two adjacent substituents of may be joined or fused to form a ring; However, R L , R M , and R N any two adjacent substituents are not joined or fused to form an indolo[3,2,1-jk]carbazole; Each R Y is H or D; R 2 and R 3at least one of comprises a chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and a boron atom; R 8 is selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof; R A ~R AO , R AT ~R BB , R 1 ~R 7 are each independently a substituent selected from the group consisting of hydrogen or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; When the compound has the structure of formula (14), at least one of the following two conditions is met: (a)R AP ~R ASare each independently selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof; R AP ~R AS at least one of is unique; only said compound contains one Si; and (b)R AP ~R AS are each independently a substituent selected from the group consisting of hydrogen or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; R AP At least one of R AQ At least one of R AR and at least one of R AS at least one of is deuterium; Any adjacent R AP ~R AS can be joined or fused to form a ring; R AP ~R AS at least one of R comprises a group selected from the group consisting of triazine, pyrimidine, pyridine, pyrazine, boryl, silane, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, tetraphenylene, biscarbazole, and combinations thereof; AP ~R AS each does not contain a six-membered ring containing exactly one B and exactly one N; However, the compound is not one of the following: [ka]

[0056] In some embodiments, X 9 ~X 113 and X 117 ~X 121 are C respectively.

[0057] In some embodiments, X 1 ~X 8 At least one of X 9 ~X 16 At least one of X 17 ~X 31 and X 122 At least one of X 32 ~X 42 At least one of X 43 ~X 53 At least one of X 54 ~X 68 At least one of X 69 ~X 83 At least one of X 84 ~X 98 At least one of X 99 ~X 113 At least one of X 114 ~X 116 At least one of X 117 ~X 121 At least one of is N and X 123 ~X 138 At least one of is N.

[0058] In some embodiments, X 1 ~X 8 One of the X 9 ~X 16 One of the X 17 ~X 31 and X 122 One of the X 32 ~X 42 One of the X 43 ~X 53 One of the X 54 ~X68 One of the X 69 ~X 83 One of the X 84 ~X 98 One of the X 99 ~X 113 One of the X 114 ~X 116 One of the X 117 ~X 121 One of them is N and the other is X 123 ~X 138 One of them is N.

[0059] In some embodiments, X 1 ~X 8 At least two of X 9 ~X 16 At least two of X 17 ~X 31 and X 122 At least two of X 32 ~X 42 At least two of X 43 ~X 53 At least two of X 54 ~X 68 At least two of X 69 ~X 83 At least two of X 84 ~X 98 At least two of X 99 ~X 113 At least two of X 114 ~X 116 At least two of X 117 ~X 121 At least two of these are N.

[0060] In some embodiments, X 1 ~X 8 Two of them, X 9 ~X 16 Two of them, X 17 ~X 31 and X 122 Two of them, X 32 ~X 42 Two of them, X 43 ~X 53 Two of them, X 54 ~X 68 Two of them, X 69 ~X83 Two of them, X 84 ~X 98 Two of them, X 99 ~X 113 Two of them, X 114 ~X 116 Two of them, X 117 ~X 121 Two of them, and X 123 ~X 138 These two are N.

[0061] In some embodiments, the maximum number of N in each ring is 1.

[0062] In some embodiments, the maximum number of N in each ring is 2.

[0063] In some embodiments, R A and R B At least one of R C , R D , and R 1 At least one of R E ~R G At least one of R I ~R K At least one of R L ~R N At least one of R O ~R Q At least one of R R and R S At least one of R T ~R W and R 4 At least one of R X ~R AA and R 5 At least one of R AB ~R AE and R 6 At least one of R AF ~R AI and R 7 At least one of R AJ , R AK , and R 8 At least one of R AL ~R AN At least one of R AP ~RAS At least one of R AT ~R AX and at least one of R AY ~R BB at least one of comprises a chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, silyl, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and a boron atom.

[0064] In some embodiments, R 1 ~R 8 is each an aryl or heteroaryl, which may be further substituted.

[0065] In some embodiments, the compound is further deuterated.

[0066] In some embodiments, the compound is at least X% deuterated, where X% is selected from the group consisting of 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. As used herein, percent deuteration has its ordinary meaning and includes the percentage of hydrogen atoms (e.g., positions that are hydrogen, deuterium, or halogen) that are replaced with deuterium atoms.

[0067] In some embodiments, the compound has formula (4), wherein (Y 2 ,Y 3 ) pair is selected from the group consisting of (O,O), (O,S), (S,S), (O,Se), (S,Se), and (Se,Se).

[0068] In some embodiments, the compound has formula (4), wherein Y 2 does not exist and Y3 is selected from the group consisting of O, S, and Se.

[0069] In some embodiments, the compound has formula (4), wherein R I ~R K At least one of comprises a moiety selected from the group consisting of carbazole and triphenylsilyl.

[0070] In some embodiments, the compound has formula (6), wherein (Y 4 ,Y 5 ) pair is selected from the group consisting of (O,O), (O,S), (S,S), (O,Se), (S,Se), and (Se,Se).

[0071] In some embodiments, the compound is of formula (6) and the compound is selected from the group consisting of: [ka]

[0072] In some embodiments, the compound is of Formula (7) or Formula (12); 2 , R 3 , and R 8 Only the substituted or unsubstituted carbazoles are included.

[0073] In some embodiments, the compound is selected from the group consisting of formulas (8), (9), (10), and (11); wherein R V At least one of R X One of them, R AB One of them, R AF One of them is D.

[0074] In some embodiments, the compound is selected from the group consisting of formulas (8), (9), (10), and (11); wherein R W , R Y , R AC , and R AG are H or D, respectively.

[0075] In some embodiments, the compound is selected from the group consisting of formulas (8), (9), (10), and (11); wherein R V , R W , R X , R Y , R AB , R AC , R AF , and R AG However, neither of them is H.

[0076] In some embodiments, the compound is selected from the group consisting of formulas (8), (9), (10), and (11), wherein only the compound contains a moiety selected from the group consisting of carbazole, phenyl, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. In some embodiments, the phenyl is attached at the meta position.

[0077] In some embodiments, the compound has formula (8), wherein R 4 contains a boryl group.

[0078] In some embodiments, the compound is of formula (9) and the compound does not have C2 symmetry.

[0079] In some embodiments, the compound is of Formula (9), and each carbazole in the compound can be bonded to another carbazole only at the 3-position of one carbazole and the 9-position of another carbazole.

[0080] In some embodiments, the compound has formula (9), wherein R 5 comprises a heteroaromatic group or a boryl group.

[0081] In some embodiments, the compound has formula (9), wherein R 5comprises a chemical group selected from the group consisting of pyridine, pyrazine, pyrimidine, pyridazine, triazine, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and a boron atom.

[0082] In some embodiments, the compound has formula (12), wherein R 8 comprises a moiety selected from the group consisting of carbazole and boryl.

[0083] In some embodiments, the compound has formula (13), wherein X 114 ~X 116 are N, respectively.

[0084] In some embodiments, the compound has formula (13), wherein R AN contains only carbazole.

[0085] In some embodiments, the compound has formula (13), wherein R AN is C X 117 The two are joined at the same position.

[0086] In some embodiments, the compound has formula (14), wherein R AP ~R AS At least one of comprises a moiety selected from the group consisting of carbazole, phenyl, pyridine, pyrazine, pyrimidine, pyridazine, triazine, and boryl.

[0087] In some embodiments, the compound has formula (15), wherein R AX R AV It bonds to form a five- or six-membered ring.

[0088] In some embodiments, the compound has formula (15), wherein X 129 is C and R AX R AV It combines with to form indole.

[0089] In some embodiments, the compound is of Formula (16) and L is selected from the group consisting of a direct bond, phenyl, biphenyl, or naphthyl.

[0090] In some embodiments, the compound has formula (16) and two R AY combines to form an indole that is fused with the carbazole of formula (16).

[0091] In some embodiments, the compound has formula (16), wherein R BB is selected from the group consisting of a direct bond, phenyl, biphenyl, or naphthyl.

[0092] In some embodiments, the compound has formula (16), wherein R AY is selected from the group consisting of carbazole or indolocarbazole.

[0093] In some embodiments, the compound is selected from the group consisting of: [ka] [ka] [ka] [ka] [ka] [ka] During the ceremony, XA1 ~X A5 are each independently C or N; Y A are each independently absent, or, if present, selected from the group consisting of O, S, Se, CRR', SiRR', NR, BR, and BRR'; each L' is independently selected from the group consisting of a direct bond, phenyl, biphenyl, and naphthyl; R A’ , R B’ , R C’ , R D’ , R E’ , R F’ , and R G’ each independently represent the maximum number of substitutions possible from mono to no substitution; R, R', R A’ , R B’ , R C’ , R D’ , R E’ , R F’ , and R G’ are each independently hydrogen or a generic substituent as defined above.

[0094] In some embodiments, the compound is selected from the group consisting of: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

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[0095] C. OLEDs and Devices of the Present Disclosure In another aspect, the present disclosure also provides an OLED device that includes a first organic layer containing a compound disclosed in the Compounds section of this disclosure.

[0096] In another embodiment, the OLED comprises an anode, a cathode, and a first organic layer disposed between the anode and the cathode, wherein the first organic layer comprises a compound selected from the group consisting of Formulas (1) through (14) disclosed in the Compounds section herein.

[0097] In some embodiments, the organic layer can be an emissive layer, and the compounds described herein can be an emissive or non-emissive dopant.

[0098] In some embodiments, the compound can be a host and the first organic layer can be an emissive layer that includes a phosphorescent emitter.

[0099] In some embodiments, the phosphorescent emitter can be a transition metal complex having at least one ligand or portion of a ligand, where the ligand is a more than bidentate ligand selected from the group consisting of: [ka] [ka] [ka] During the ceremony, T is selected from the group consisting of B, Al, Ga, and In; Y 1 ~Y 13 are each independently selected from the group consisting of carbon and nitrogen; Y' is BR e , B.R. e R f , N.R. e , PR e , P(O)R e, O, S, Se, C=O, C=S, C=Se, C=NR e , C=CR e R f , S=O, SO2, CR e R f , SiR e R f , and GeR e R f selected from the group consisting of: R e and R f can be fused or linked to form a ring; R a , R b , R c , and R d each independently represents zero, mono, or up to the maximum number of substitutions allowed for its associated ring; R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e , and R f are each independently a substituent selected from the group consisting of hydrogen or deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and the general substituents defined herein; R a , R b , R c , R d , R e , and R f Any adjacent substituents of can be fused or linked to form a ring or to form a multidentate ligand.

[0100] In some embodiments, the compound can be an acceptor, and the OLED can further include a sensitizer selected from delayed fluorescent emitters, phosphorescent fluorophores, and combinations thereof.

[0101] In some embodiments, the compound can be a fluorescent emitter, a delayed fluorescent emitter, or a component of an exciplex that is a fluorescent emitter or a delayed fluorescent emitter.

[0102] In yet another embodiment, the OLED of the present disclosure can also include a light-emitting region comprising a compound disclosed in the Compounds section of this disclosure.

[0103] In some embodiments, the light-emitting region can include a compound selected from the group consisting of formulas (1) through (14) described herein.

[0104] In some embodiments, at least one of the anode, cathode, or additional layers disposed on the organic light-emitting layer functions as an enhancement layer. The enhancement layer includes a plasmonic material that nonradiatively couples to the emitter material and exhibits a surface plasmon resonance that transfers excited-state energy from the emitter material to a nonradiative mode of surface plasmon polaritons. The enhancement layer is disposed within a threshold distance from the organic light-emitting layer, and the emitter material has a total nonradiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer, and at the threshold distance, the total nonradiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further includes an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the enhancement layer opposite the organic light-emitting layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the enhancement layer from the light-emitting layer, but still outcouples energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered into free space as photons. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device, such as, but not limited to, an organic waveguide mode, a substrate mode, or another waveguide mode. If the energy is scattered into a non-free-space mode of the OLED, other outcoupling schemes can be incorporated to extract the energy into free space. In some embodiments, one or more intervening layers can be disposed between the enhancement layer and the outcoupling layer. Examples of intervening layers can be dielectric materials, including organic, inorganic, perovskite, and oxide, and can include stacks and / or mixtures of these materials.

[0105] Enhancement layers alter the effective properties of the medium in which the emitter material resides, resulting in any or all of the following: a reduction in the emission rate; a change in the emission line shape; a change in the emission intensity with angle; a change in the stability of the emitter material; a change in the efficiency of the OLED; and a reduction in the efficiency roll-off of the OLED device. Placing an enhancement layer on the cathode side, the anode side, or both can result in an OLED device that utilizes any of the above-described effects. In addition to the specific functional layers shown in the various OLED examples described and illustrated herein, OLEDs according to the present disclosure can include any of the other functional layers frequently found in OLEDs.

[0106] The enhancement layer can be composed of a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. As used herein, a plasmonic material is a material whose real part of its permittivity crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material includes at least one metal. In such embodiments, the metal can include at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. In general, a metamaterial is a medium composed of different materials such that the medium as a whole behaves differently from the sum of its parts. In particular, an optically active metamaterial is defined as a material that has both a negative permittivity and a negative magnetic permeability. On the other hand, a hyperbolic metamaterial is an anisotropic medium in which the permittivity or permeability has different signs in different spatial directions. Optically active metamaterials and hyperbolic metamaterials are distinct from many other photonic structures, such as distributed Bragg reflectors ("DBRs"), in that they are media that appear uniform in the direction of propagation on the length scale of the wavelength of light. Using terminology understood by those skilled in the art, the dielectric constant of a metamaterial in the direction of propagation can be described by an effective medium approximation. Plasmonic materials and metamaterials offer a way to control the propagation of light and can improve OLED performance in a variety of ways.

[0107] In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has periodically, quasi-periodically, or randomly arranged wavelength-sized features or periodically, quasi-periodically, or randomly arranged sub-wavelength-sized features. In some embodiments, the wavelength-sized features and sub-wavelength-sized features have sharp edges.

[0108] In some embodiments, the outcoupling layer has periodically, quasi-periodically, or randomly arranged wavelength-sized features or periodically, quasi-periodically, or randomly arranged subwavelength-sized features. In some embodiments, the outcoupling layer can be composed of nanoparticles, and in other embodiments, the outcoupling layer is composed of nanoparticles disposed on a material. In these embodiments, outcoupling can be tunable by at least one of varying the size of the nanoparticles, varying the shape of the nanoparticles, varying the material of the nanoparticles, adjusting the thickness of the material, varying the refractive index of the material or the refractive index of an additional layer disposed on the nanoparticles, varying the thickness of an enhancement layer, and / or varying the material of the enhancement layer. The nanoparticles of the device can be formed from at least one of a metal, a dielectric material, a semiconductor material, an alloy of a metal, a mixture of dielectric materials, a stack or layer of one or more materials, and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles, the metal being selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. The nanoparticles can have additional layers disposed thereon. In some embodiments, the polarization of the emitted light can be adjusted using the outcoupling layer. By varying the dimensions and periodicity of the outcoupling layer, the type of polarization that is preferentially outcoupled to air can be selected. In some embodiments, the outcoupling layer also functions as an electrode for the device.

[0109] In yet another aspect, the present disclosure also provides a consumer product comprising an OLED having an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound disclosed in the Compounds section of this disclosure.

[0110] In some embodiments, the consumer product comprises an organic light emitting device (OLED) having an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer can comprise a compound selected from the group consisting of Formulas (1) through (14) described herein.

[0111] In some embodiments, the consumer product can be one 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 less than 2 inches in diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall including multiple displays aligned together, a theater or stadium screen, a light therapy device, and a sign.

[0112] 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.

[0113] Some OLED materials and configurations are described in US Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated by reference in their entireties.

[0114] 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.

[0115] 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," Nature, 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.

[0116] 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 are incorporated by reference.

[0117] 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 with 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.

[0118] 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 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides an example of how some layers can be omitted from the structure of device 100.

[0119] 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 disclosure 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 a mixture of a host and a dopant, or more generally, a mixture, 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 include a single layer, or may further include multiple layers of different organic materials, such as those described with respect to Figures 1 and 2.

[0120] 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 the mesa structure described in U.S. Pat. No. 6,091,195 to Forrest et al. and / or the recessed structure described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0121] 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 entirety; 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) (also referred to as organic vapor jet deposition (OVJD)), 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 patterning through a mask, 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 organic vapor jet printing (OVJP). 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, 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.

[0122] Devices fabricated according to embodiments of the present disclosure 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.

[0123] Devices made according to embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into various electrical products or intermediate components. Such electrical products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels), and the like, which can be utilized by end-user product manufacturers. Such electronic component modules can optionally include drive electronics and / or power sources. Devices made according to embodiments of the present disclosure can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. Consumer products are disclosed that include OLEDs that include compounds of the present disclosure in the organic layer of the OLED. Such consumer products include any type of product that includes one or more light sources and / or one or more visual displays of some kind. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor illumination and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable 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, vehicles, video walls including multiple displays aligned together, theater or stadium screens, light therapy devices, and signage. A variety of control mechanisms, including passive matrix and active matrix, can be used to control devices fabricated according to the present disclosure. 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 can also be used outside this temperature range, e.g., between -40°C and +80°C.

[0124] Further details regarding OLEDs and the definitions set forth above can be found in US Pat. No. 7,279,704, which is incorporated by reference in its entirety.

[0125] 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.

[0126] In some embodiments, the OLED has one or more properties selected from the group consisting of flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

[0127] In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises an RGB pixel array or a white and color filter pixel array. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0128] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can generate luminescence via phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF) (also known as E-type delayed fluorescence; see, e.g., U.S. Application No. 15 / 700,352, incorporated by reference in its entirety), triplet-triplet annihilation, or a combination of these processes. In some embodiments, the emissive dopant can be a racemic mixture or enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from the others). When more than one ligand is present that coordinates to the metal, in some embodiments, the ligands can all be the same. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, all of the ligands can be different from each other. This is true even in embodiments where a ligand coordinated to a metal can combine with other ligands coordinated to the metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligand. Thus, when the coordinating ligands are bonded to one another, in some embodiments, all of the ligands can be identical, while in some other embodiments, at least one of the bonded ligands can be different from the other ligands.

[0129] In some embodiments, the compounds can be used as one component of an exciplex used as a sensitizer.

[0130] In some embodiments, the sensitizer is a single component or one of multiple components that form an exciplex.

[0131] According to another aspect, compositions comprising the compounds described herein are also disclosed.

[0132] 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.

[0133] In yet another aspect of the present disclosure, there is provided a composition comprising the novel compounds disclosed herein. The composition may also comprise one or more components selected from the group consisting of a solvent, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material disclosed herein.

[0134] The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure, or monovalent or polyvalent variants thereof. In other words, the compounds of the present invention, or monovalent or polyvalent variants thereof, can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of monomers, polymers, macromolecules, and supramolecules (also known as supermolecules). As used herein, a "monovalent variant of a compound" refers to a moiety that is identical to the compound except that one hydrogen has been removed and replaced with a bond to the remainder of the chemical structure. As used herein, a "polyvalent variant of a compound" refers to a moiety that is identical to the compound except that more than one hydrogen has been removed and replaced with a bond to the remainder of the chemical structure. In the example of a supramolecule, the compounds of the present invention can also be incorporated into the supramolecular complex without a covalent bond.

[0135] D. Combinations of Compounds of the Present Disclosure with Other Materials 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.

[0136] a) Conductive (electrically 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.

[0137] 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, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012 [ka] [ka]

[0138] b) HIL / HTL: The hole injection / transport material used in the present disclosure is not particularly limited, and any compound may be used as long as it is a compound 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.

[0139] Examples of aromatic amine derivatives used in the HIL or HTL include, but are not limited to, the following general structures: [ka]

[0140] Ar 1 From Ar 9each of which is 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, indoxazole, and aromatic heterocyclic compounds such as benzothiazole, 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 cyclic 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 Ar can be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0141] In one embodiment, Ar 1 From Ar9 teeth, [ka] (wherein 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 groups as defined above.

[0142] 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 bound to the metal; and k' + k'' is the maximum number of ligands that can be bound to the metal.

[0143] 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.

[0144] 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]

[0145] c) EBL: 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 used as one of the hosts described below.

[0146] d) Host: 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 contain a host material using the metal complex as a dopant material. The host material is not particularly limited, and any metal complex or organic compound can be used as long as the triplet energy of the host is higher than that of the dopant. Any host material can be used with any dopant as long as the triplet criterion is met.

[0147] 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 bound to the metal; and k' + k'' is the maximum number of ligands that can be bound to the metal.

[0148] In one embodiment, the metal complex is: [ka] where (ON) is a bidentate ligand with the metal coordinated to atoms O and N.

[0149] In another embodiment, Met is selected from Ir and Pt. 103 -Y 104 ) is a carbene ligand.

[0150] In one embodiment, the host compound is selected from the group consisting of 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, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazoline, and aromatic heterocyclic compounds such as benzofuropyridine, 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 cyclic groups and aromatic heterocyclic groups, which may be the same or different groups and which have 2 to 10 cyclic structural units 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 within each group can be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0151] In one embodiment, the host compound contains at least one of the following groups in the molecule: [ka] [ka] In the formula, R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, 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. k is an integer from 0 to 20 or from 1 to 20. X 101 ~X 108 is independently selected from C (including CH) or N. Z 101 and Z 102 is independently, NR 101 , O, or S.

[0152] 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, KR20130115564 , TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US2 0090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012 126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO200706375 4. WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO20100 56066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO 2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, US9466803

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[0153] e) Additional luminaries: 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.Examples of 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.

[0154] 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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[0155] f) HBL: 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.

[0156] In one embodiment, the compounds used in the HBL contain the same molecules or the same functional groups as those used in the hosts described above.

[0157] In another embodiment, the compound used in the HBL comprises 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.

[0158] g)ETL: 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.

[0159] 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, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, 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.

[0160] 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 bound to the metal.

[0161] 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, W O2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535 [ka] [ka] [ka]

[0162] h) Charge Generation Layer (CGL) 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.

[0163] In any of the above-mentioned compounds used in each layer of an OLED device, the hydrogen atoms may be partially or fully deuterated. The minimum amount of hydrogen in a deuterated compound is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. Thus, any specifically recited substituent, such as, but not limited to, methyl, phenyl, pyridyl, etc., can be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents, such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc., can be undeuterated, partially deuterated, and fully deuterated versions thereof.

[0164] 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.

[0165] Experimental Section Synthesis of Int.D1-1: [ka]

[0166] Step 1: Cesium carbonate (84 g, 257 mmol, 3.0 equiv.) was added to a solution of carbazole-d8 (15 g, 86 mmol, 1.0 equiv.) and 1-bromo-2-fluorobenzene-3,4,5,6-d4 (30.6 g, 171 mmol, 2.0 equiv.) in N,N-dimethylformamide (143 mL). After heating at 135 °C for 48 h, the mixture was cooled to room temperature (RT), diluted with water, and extracted with methyl tert-butyl ether. The combined organic layer was washed sequentially with 1 M HCl, water, and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was absorbed onto Celite (diatomaceous earth) and purified by column chromatography eluting with dichloromethane in hexane to give 9-(2-bromophenyl-3,4,5,6-d4)-9H-carbazole-1,2,3,4,5,6,7,8-d8 (15.6 g, 55% yield) as an off-white solid.

[0167] Step 2: A 1.6 M solution of n-butyllithium in hexane (34.8 mL, 55.6 mmol, 1.2 equiv.) was added dropwise to a solution of 9-(2-bromophenyl-3,4,5,6-d4)-9H-carbazole-1,2,3,4,5,6,7,8-d8 (15.5 g, 46.4 mmol, 1.0 equiv.) in THF (180 mL) at -78 °C and stirred for 2 h. Trimethylborate (15.5 mL, 139 mmol, 3.0 equiv.) was added dropwise, and the reaction was allowed to warm gradually to RT. After overnight, the reaction mixture was quenched with water and extracted with ethyl acetate. The organic layer was washed sequentially with 1 M HCl, water, and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. Hexane was added to the residue, and the suspension was stirred overnight at RT. The resulting solid was filtered and dried under vacuum at 40° C. for 12 hours to give (2-(9H-carbazol-9-yl-d8)phenyl-3,4,5,6-d4)boronic acid (Int DH1-1) (12 g, 86% yield) as a white solid.

[0168] Synthesis of DH1: [ka]

[0169] Step 1: Potassium carbonate (69.6 g, 504 mmol, 3.0 equiv.) was added to a mixture of compound 1-bromo-2-fluorobenzene-d4 (31 g, 168 mmol, 1.0 equiv.) and Int DH1-1 (55.3 g, 185 mmol, 1.1 equiv.) in a mixture of 1,4-dioxane (700 mL) and water (140 mL). The mixture was sparged with nitrogen for 10 minutes. SphosPd-G2 (6.05 g, 8.40 mmol, 0.05 equiv.) was added with continued sparging. After heating at 81 °C overnight, the reaction mixture was cooled to RT and diluted with ethyl acetate. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with saturated aqueous brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was absorbed onto silica gel and purified by column chromatography eluting with dichloromethane in heptane to give Int DH1-2 (45 g, 76% yield) as a white solid. [ka]

[0170] Step 2: A mixture of Int DH1-2 (45 g, 127 mmol, 1 equiv.), Int DH1-3 (48.7 g, 140 mmol, 1.1 equiv.), and cesium carbonate (124 g, 382 mmol, 3 equiv.) in N-methyl-2-pyrrolidinone (600 mL) was heated at 180° C. for 7 days. After cooling to RT, the reaction mixture was diluted with ethyl acetate and water. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography eluting with dichloromethane in heptane to give DH1 (62 g, 71% yield) as a white solid.

[0171] Synthesis of Int.D2-1: [ka]

[0172] A 1.6 M solution of n-butyllithium in hexane (50.3 mL, 80 mmol, 0.94 equiv.) was added dropwise to a solution of carbazole-d8 (15 g, 86 mmol, 1.0 equiv.) in THF (500 mL) at 0 °C. The resulting mixture was warmed to RT and stirred for 15 min. This mixture was slowly transferred via cannula to a solution of 2,4,6-trichloro-1,3,5-triazine (7.42 g, 40.2 mmol, 0.47 equiv.) in THF (200 mL) at RT. After heating at 60 °C for 6 h, the reaction mixture was cooled to RT, quenched with water, ethyl acetate was added, and the layers were separated. The organic layer was concentrated under reduced pressure and then treated with diethyl ether. The resulting precipitate was filtered and washed with warm ethanol to give Int. D2-1 as an off-white solid (15 g, 23% yield).

[0173] Synthesis of Int.D2-2: [ka]

[0174] Step 1: The reaction was carried out under a nitrogen atmosphere. A solution of bromobenzene-d5 (166 g, 1.02 mol, 3.05 eq) in 1500 mL of dry THF in a 3 L three-neck flask was cooled to -75 °C. n-BuLi (373 mL, 2.74 M, 1.02 mol, 3.05 eq) was added dropwise below -71 °C. After the addition, the reaction was stirred at -74 °C for 1.5 h. The resulting solution was transferred via cannula under nitrogen to a solution of SiCl4 (57 g, 38.4 mL, 0.336 mol, 1.0 eq) in 400 mL of dry THF at below -70 °C over 70 min. The reaction was allowed to warm to RT overnight. The solvent was removed in vacuo, toluene was added to the residue, and the mixture was stirred for 30 min, filtered, and concentrated under reduced pressure. Heptane was added to the residue, stirred overnight, filtered, and washed with heptane. The solid was dried under high vacuum to give the product Ph3Cl-d 15 was obtained as a white solid (69 g, 66.4% yield).

[0175] Step 2: The reaction was carried out under a nitrogen atmosphere. A solution of 1,3-dibromobenzene-d4 (231 g, 0.965 mol, 1.3 equiv.) in 3600 mL of dry THF in a 12 L three-neck flask was cooled to -73 °C. n-BuLi (356 mL, 0.965 mol, 1.3 equiv., 2.71 M) was added dropwise over 100 min. After addition, the solution was stirred for 1.5 h. Ph3Cl-d 15 A solution of (230 g, 0.742 mol, 1 equiv.) in 900 mL of dry THF was added via a dropping funnel over 20 minutes at below -68°C. After stirring overnight, the reaction was quenched with water and diluted with ethyl acetate. The organic layer was separated, washed with brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. Methanol was added to the residue, the solution was stirred, and the precipitate was collected by filtration and dried under vacuum to give the product (3-bromophenyl-2,4,5,6-d4)tris(phenyl-d5)silane as a white solid (267.5 g, 84% yield).

[0176] Step 3: (3-Bromophenyl-2,4,5,6-d4)tris(phenyl-d5)silane (290 g, 0.667 mol, 1.0 equiv.), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (254 g, 1.0 mol, 1.5 equiv.), and KOAc (197 g, 2.0 mol, 3 equiv.) were added to 2.4 L of DMF in a 5 L three-neck flask under nitrogen. The mixture was purged with nitrogen, and PdCl2(dppf)2 (10.9 g, 13.35 mmol, 0.02 equiv.) was added, and the mixture was heated at 115 °C for 10 h. The reaction was cooled to RT, and ice water was added in portions with stirring. The mixture was stirred, filtered, washed with water, and dried under vacuum to give a crude residue. The crude residue was dissolved in DCM and eluted through a silica plug, then concentrated under reduced pressure. Heptane was added, the precipitate collected, and the solid washed with heptane and then dried under vacuum to give tris(phenyl-d5)(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl-2,4,5,6-d4)silane, Int DH2-2, as an off-white solid (265 g, 82% yield).

[0177] Synthesis of DH2: [ka]

[0178] Toluene (180 mL) and ethanol (90 mL) were added to a mixture of Int DH2-2 (10 g, 20.76 mmol), Int DH2-1 (9.11 g, 19.73 mmol, RI21354), and Na2CO3 (6.60 g, 62.3 mmol). Nitrogen was bubbled through the suspension for 10 minutes, after which tetrakis(triphenylphosphine)Pd(0) (1.2 g, 1.038 mmol) and water (54 mL) were added. The mixture was bubbled with nitrogen for an additional 5 minutes, sealed with a septum, heated to 80 °C, and stirred overnight. A second batch was run on the same scale. The two batches were combined and extracted with ethyl acetate. The combined organic layers were rotovapped to dryness. The crude material was dissolved in dichloromethane and filtered through a silica pad, eluting with dichloromethane to give DH2 as a white solid (30 g, 92% yield).

[0179] Synthesis of DH3: [ka]

[0180] Step 1: A mixture of 2-bromo-5-chloro-1,3-difluorobenzene-4,6-d2 (200 g, 872 mmol, 1 equiv.), phenol-d5 (259 g, 2.6 mol, 3 equiv.), and potassium carbonate (361 g, 2.6 mol, 3 equiv.) in anhydrous N-methyl-2-pyrrolidone (2 L) was stirred at 100 °C for 72 h. After cooling to room temperature, water (2 L) was added dropwise to produce a precipitate. The precipitate was filtered, washed with water, and dried overnight at 40 °C to give 1,1'-((2-bromo-5-chloro-1,3-phenylene-4,6-d2)bis(oxy))bis(benzene-2,3,4,5,6-d5) (222 g, 66% yield) as an off-white solid.

[0181] Step 2: 1,1'-((2-bromo-5-chloro-1,3-phenylene-4,6-d2)bis(oxy))bis(benzene-2,3,4,5,6-d5) (222 g, 573 mmol, 1 equiv.) was dissolved in anhydrous m-xylene (2 L) and sparged with nitrogen for 15 minutes. The mixture was cooled to -45°C, and a 2.5 M solution of n-butyllithium in hexanes (252 mL, 630 mmol, 1.1 equiv.) was added dropwise, maintaining the temperature below -38°C. The mixture was allowed to warm to room temperature and then heated at 60°C for 3 hours. The mixture was cooled to -45°C, and boron tribromide (172 g, 687 mmol, 1.2 equiv.) was added dropwise. The mixture was allowed to warm to room temperature and stirred overnight. N,N-Diisopropylethylamine (185 g, 1.4 mol, 2.5 equiv.) was added at room temperature, and the reaction was heated at 150 °C for 3 h. After cooling to room temperature, water (2 L) was added dropwise to form a precipitate. The precipitate was filtered, washed with water, and dried under vacuum at 50 °C overnight to give Int DH3-1 (108 g, 60% yield) as a white solid. [ka]

[0182] Step 3: Tris(dibenzylideneacetone)dipalladium (0.79 g, 0.86 mmol, 0.01 equiv.) and tri-tert-butylphosphine tetrafluoroborate (0.37 g, 1.3 mmol, 0.015 equiv.) were dissolved in toluene (860 mL) and sparged with nitrogen for 15 minutes. Int DH3-1 (30.0 g, 95 mmol, 1.1 equiv.), Int DH3-2 (30.0 g, 86 mmol, 1.0 equiv.), and sodium tert-butoxide (9.96 g, 104 mmol, 1.2 equiv.) were added to the reaction, which was then heated to reflux overnight. The reaction was cooled to room temperature and diluted with water. The mixture was extracted three times with dichloromethane, and the combined organic layers were concentrated under reduced pressure. The resulting solid was redissolved in dichloromethane and passed through a plug of silica (500 g) eluting with dichloromethane. The dichloromethane solution was concentrated under reduced pressure to give an off-white solid, which was dried overnight at 50° C. to give crude DH3 (51.2 g, 95% yield). 30 g of the crude material was purified by column chromatography eluting with 40% dichloromethane in hexanes, followed by recrystallization in toluene to give DH3 as a white solid (11.4 g, 38% yield).

[0183] Synthesis of DH4: [ka]

[0184] A solution of potassium carbonate (7.1 g, 51.5 mmol, 3.3 equiv) in water (12 mL) was added to a solution of Int DH2-1 (11.9 g, 15.4 mmol, 1.0 equiv) and Int DH1-1 (7.7 g, 25.7 mmol, 1.7 equiv) in 1,4-dioxane (40 mL). The mixture was sparged with nitrogen for 5 minutes. Tetrakis(triphenylphosphine)palladium(0) (3.0 g, 2.6 mmol, 0.17 equiv) was added. After heating at 72 °C overnight, the reaction mixture was cooled to RT and then diluted with dichloromethane and THF. The organic layer was washed with water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was absorbed onto Celite and purified by column chromatography eluting with dichloromethane in hexane to give DH4 (3.63 g, 35% yield) as a white solid.

[0185] Synthesis of DH5: [ka]

[0186] Step 1: A suspension of carbazole-d8 (9.6.0 g, 54.7 mmol, 1.4 equiv.) in dry m-xylene (250 mL) was sparged with nitrogen for 30 min and then cooled to 0 °C. 3 M methylmagnesium bromide in THF (17.0 mL, 50.8 mmol, 1.3 equiv.) was added dropwise, and the mixture was stirred at 0 °C for 1 h. Separately, (allyl)palladium chloride (0.19 g, 0.51 mmol, 0.013 equiv.) and bis(1,1-dimethylethyl)(1-methyl-2,2-diphenylethenyl)phosphine (vBRIDP) (0.66 g, 1.9 mmol, 0.05 equiv.) were added to a 40 mL vial that had been purged with nitrogen three times. Dry m-xylene (15 mL) was added, and the solution was stirred for 15 min. The catalyst mixture was then added to the reaction mixture, followed by 1-bromo-2-fluorobenzene-d4 (7.0 g, 39.1 mmol, 1.0 equiv). The reaction mixture was then heated to 100° C. After stirring overnight, the reaction was cooled to RT, quenched with water, and diluted with dichloromethane. The layers were separated, and the aqueous layer was extracted with dichloromethane. The combined organic layers were washed with saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was loaded onto Celite and purified by column chromatography eluting with dichloromethane in hexane to give 9-(2-fluorophenyl)-9H-carbazole-d 12 (6.2 g, 58% yield) was obtained as a white solid.

[0187] Step 2: 9-(2-fluorophenyl)-9H-carbazole-d 12 (4.0 g, 14.6 mmol, 1.0 equivalent), 3,9'-biscarbazole-d 15A solution of 1,3-dimethyl-2,4-dichloromethane (6.1 g, 17.6 mmol, 1.5 equiv.) and cesium carbonate (14.3 g, 43.9 mmol, 3.0 equiv.) in N-methylpyrrolidinone (80 mL) was sparged with nitrogen for 30 minutes and then heated at 130° C. overnight. The reaction mixture was cooled to RT and diluted with ethyl acetate and water. The layers were separated and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with saturated brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was loaded onto Celite and purified by column chromatography eluting with dichloromethane in hexane to give compound DH5 (7.5 g, 85% yield) as a white solid.

[0188] Synthesis of DH6: [ka]

[0189] Step 1: Int DH1-1 (5.37 g, 17.9 mmol, 1.1 equiv.) was added to a solution of 2,6-dichloro-4-iodopyridine-3,5-d2 (4.5 g, 16.3 mmol, 1.0 equiv.) in acetonitrile-d3 (54 mL), and the solution was sparged with nitrogen for 5 minutes. A solution of sodium carbonate (5.2 g, 48.9 mmol, 3.0 equiv.) in DO (36 mL) and dichlorobis(triphenylphosphine)palladium(II) (1.15 g, 1.63 mmol, 0.1 equiv.) were added while continuing to sparge for an additional 5 minutes. The mixture was kept at 72 °C overnight. The reaction mixture was cooled to RT and diluted with dichloromethane. The layers were separated, and the organic layer was washed with water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography loaded onto Celite and eluted with dichloromethane in hexane to give 9-(2-(2,6-dichloropyridin-4-yl-3,5-d2)phenyl-3,4,5,6-d4)-9H-carbazole-1,2,3,4,5,6,7,8-d8 (5.45 g, 83% yield) as an off-white solid.

[0190] Step 2: Dry THF (100 mL) was added to sodium tert-butoxide (2.83 g, 29.5 mmol, 2.2 equiv.) while sparging with nitrogen, followed by carbazole-d8 (5.16 g, 29.5 mmol, 2.2 equiv.). The mixture was stirred at RT for 5 min. A solution of 9-(2-(2,6-dichloropyridin-4-yl-3,5-d2)phenyl-3,4,5,6-d4)-9H-carbazole-1,2,3,4,5,6,7,8-d83 (5.4 g, 13.4 mmol, 1.0 equiv.) in THF (50 mL) was added while continuing to sparge with nitrogen, followed by SphosPd-G2 (1.93 g, 2.7 mmol, 0.2 equiv.). The reaction mixture was heated at 72 °C overnight. The reaction mixture was cooled to RT and quenched with water. Dichloromethane was added, and the mixture was filtered through a Celite pad. The filtrate was transferred to a separatory funnel, and the layers were separated. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was packed onto silica gel and purified by column chromatography eluting with dichloromethane in hexane. The fractions were concentrated and recrystallized from toluene to give DH6 (5.0 g, 55% yield) as a white solid.

[0191] OLEDs were grown on glass substrates precoated with an indium tin oxide (ITO) layer with a sheet resistance of 15-Ω / sq. Prior to deposition or coating of the organic layers, the glass substrates were degreased with solvent and then treated with oxygen plasma at 50 W and 100 mTorr for 1.5 minutes and UV ozone for 5 minutes. The devices were then vacuum-sealed under high vacuum (<10 -6 The devices were fabricated by thermal evaporation at 1000 Å (2000 Å) pressure (torr). The anode electrode was indium tin oxide (ITO) 750 Å. All devices were encapsulated with a glass lid sealed with epoxy resin in a nitrogen glove box (<1 ppm H2O and O2) immediately after fabrication using a moisture getter inside the package. Doping percentages are in volume percent. Devices were grown in several different device configurations using the following materials: [ka] [ka]

[0192] Examples 1 to 7 and Comparative Examples 1 to 7 had organic layers consisting of, from the ITO surface, a 100 Å thick HIL (HIL), a 250 Å thick HTL (HTL), a 50 Å thick EBL, a 300 Å thick host doped with X% Host 2, a 12% Pt-2 EML (EML), a 50 Å thick BL, a 300 Å thick ETL (ETL) doped with 35% Compound 4, and a 10 Å thick EIL (EIL), as well as a 1,000 Å thick Al cathode. The EBL, Host 1, Host 2, and Host 2 concentrations for each Example and Comparative Example device are shown in Table 1. Table 1: Materials used in each device [Table 1]

[0193] In each of Examples 1 to 6 and Comparative Examples 1 to 6, the measured life (LT90) was 2 The relative LT90 of Example 1 is the time it takes for the luminance to decrease to 90% of the initial luminance at a constant current density. The lifetime of each example is reported relative to the corresponding comparative example device. For example, the relative LT90 of Example 1 is the ratio of the LT90 of Example 1 to the LT90 of Comparative Example 1. Relative LT90 for devices containing deuterated hosts [Table 2]

[0194] The data show that Device Examples 1-6 each exhibited longer lifetimes than their respective comparison compounds. The 30%-100% lifetime improvements exceed any values ​​that could be attributed to experimental error, making the observed improvements significant. The significant performance improvements seen in the data were unexpected, given that the devices have identical structures except that one of the hosts in the emissive layer is deuterated. Without being bound by any theory, it is believed that this improvement may be due to suppression of intermolecular decomposition between the deuterated host and the dopant.

Claims

1. A compound selected from the group consisting of formulas (13), (14), (9), (5), (1), (2), (3), (4), (6), (7), (8), (10), (11), (12), (15), and (16) shown below. 【Chemistry 1】 (In the formula, R ＡＬ and R ＡＭ and at least one of R ＡＮ At least one of is D. 【Chemistry 2】 【Transformation 3】 (In the formula, R Ｘ and R Ｙ At least one of the following is D. 【Chemistry 4】 (In the formula, R Ｌ , R Ｍ , and R Ｎ At least one of is D. 【Transformation 5】 (In the formula, R Ａ and at least one of R Ｂ At least one of is D. 【Transformation 6】 (In the formula, R Ｃ and R Ｄ At least one of is D. 【Transformation 7】 (In the formula, R Ｅ , R Ｆ , R Ｇ , and R Ｈ At least one of is D. 【Transformation 8】 (In the formula, R Ｉ , R Ｊ , and R Ｋ At least one of is D. 【Chemistry 9】 (In the formula, R Ｏ , R Ｐ , and R Ｑ At least one of is D. 【Chemistry 10】 (In the formula, R Ｒ and R Ｓ At least one of is D. 【Chemistry 11】 (In the formula, R Ｔ , R Ｕ , R Ｖ , and R Ｗ At least one of is D. 【Chemistry 12】 (In the formula, R ＡＢ and R ＡＣ At least one of the following is D. 【Chemistry 13】 (In the formula, R ＡＦ and R ＡＧ At least one of is D. 【Chemistry 14】 【Chemistry 15】 (In the formula, R ＡＴ , R ＡＵ , R ＡＶ , and R ＡＷ At least one of is D. 【Chemistry 16】 (In the formula, R ＡＹ and R ＡＺ at least one of which is D; During the ceremony: R Ａ ~R ＢＢ each independently represents the maximum number of substitutions possible from mono or represents no substitution; X １ ~X １３８ are each independently C or N; X １ ~X ８ At least one of １１４ ~X １１６ one of which is N; X ３２ and X ３４ at least one of is C; Y １ ~Y ５ are each independently selected from the group consisting of O, S, and Se; Y ２ and Y ３ may represent no bond; L is a direct bond or an organic linker; R Ｅ , R Ｆ , R Ｇ , and R Ｈ at least one of is selected from the group consisting of aryl, heteroaryl, amino, silyl, boryl, and combinations thereof; R Ａ ~R Ｓ , R ＡＬ ~R ＡＯ , R ＡＹ , R ＡＺ , R ＢＡ , and R ＢＢ any two adjacent substituents of R may be joined or fused to form a ring; Ｌ , R Ｍ , and R Ｎ any two adjacent substituents of are not joined or fused to form an indolo[3,2,1-jk]carbazole; Each R Ｙ is H or D; R ２ and R ３ at least one of comprises a chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and a boron atom; R ８ is selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof; R Ａ ~R ＡＯ , R ＡＴ ~R ＢＢ , R １ ~R ７ are each independently hydrogen or a generic substituent as defined above; When the compound has the structure of formula (14), at least one of the following two conditions is met: (a) R ＡＰ ~R ＡＳ are each independently selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof; R ＡＰ ~R ＡＳ is unique; only said compound contains one Si; and (b) R ＡＰ ~R ＡＳ are each independently a substituent selected from the group consisting of hydrogen or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; R ＡＰ At least one of R ＡＱ One of them, R ＡＲ One of, and R ＡＳ is deuterium; any adjacent R ＡＰ ~R ＡＳ can be linked or fused to form a ring; R ＡＰ ~R ＡＳ at least one of comprises a group selected from the group consisting of triazine, pyrimidine, pyridine, pyrazine, boryl, silane, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, tetraphenylene, biscarbazole, and combinations thereof; However, R ＡＰ ~R ＡＳ each does not contain a six-membered ring containing exactly one B and exactly one N; However, the compound is not one of the following: 【Chemistry 17】

2. X ９ ~X １１３ and X １１７ ~X １２１ and each is C.

3. X １ ~X ８ At least one of X ９ ~X １６ At least one of X １７ ~X ３１ and X １２２ At least one of X ３２ ~X ４２ At least one of X ４３ ~X ５３ At least one of X ５４ ~X ６８ At least one of X ６９ ~X ８３ At least one of X ８４ ~X ９８ At least one of X ９９ ~X １１３ At least one of X １１４ ~X １１６ and at least one of X １１７ ~X １２１ The compound of claim 1 , wherein at least one of is N.

4. R Ａ and R Ｂ At least one of R Ｃ , R Ｄ , and R １ At least one of R Ｅ ~R Ｇ At least one of R Ｉ ~R Ｋ At least one of R Ｌ ~R Ｎ At least one of R Ｏ ~R Ｑ At least one of R Ｒ and R Ｓ At least one of R Ｔ ~R Ｗ and R ４ At least one of R Ｘ ~R ＡＡ and R ５ At least one of R ＡＢ ~R ＡＥ and R ６ At least one of R ＡＦ ~R ＡＩ and R ７ At least one of R ＡＪ , R ＡＫ , and R ８ At least one of R ＡＬ ~R ＡＮ and R ＡＰ ~R ＡＳ 2. The compound of claim 1, wherein at least one of comprises a chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, silyl, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and a boron atom.

5. 2. The compound of claim 1, wherein the compound is at least X% deuterated, where X% is selected from the group consisting of 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%.

6. The compound is of formula (4), wherein (Y ２ , Y ３ ) pair is selected from the group consisting of (O,O), (O,S), (S,S), (O,Se), (S,Se), and (Se,Se); the compound is of formula (4), wherein Y ２ does not exist, and Y ３ is selected from the group consisting of O, S, and Se; or the compound is of formula (4), wherein R Ｉ ~R Ｋ 2. The compound of claim 1, wherein at least one of comprises a moiety selected from the group consisting of carbazole and triphenylsilyl.

7. The compound is represented by formula (7) or formula (12), wherein each R ２ , R ３ , and R ８ only contains a substituted or unsubstituted carbazole; or the compound is of formula (8), and R ４ The compound of claim 1 , wherein comprises a boryl group.

8. The compound is represented by formula (12), and R 8 2. The compound of claim 1, wherein comprises a moiety selected from the group consisting of carbazole and boryl.

9. The compound is represented by formula (14), and R ＡＰ ~R ＡＳ 2. The compound of claim 1, wherein at least one of comprises a moiety selected from the group consisting of carbazole, phenyl, pyridine, pyrazine, pyrimidine, pyridazine, triazine, and boryl.

10. 2. The compound of claim 1, wherein the compound is selected from the group consisting of: [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】 (In the formula, X Ａ１ ~X Ａ５ are each independently C or N; Y Ａ are each independently absent, or, if present, selected from the group consisting of O, S, Se, CRR', SiRR', NR, BR, and BRR'; each L' is independently selected from the group consisting of a direct bond, phenyl, biphenyl, and naphthyl; R Ａ’ , R Ｂ’ , R Ｃ’ , R Ｄ’ , R Ｅ’ , R Ｆ’ , and R Ｇ’ each independently represents the maximum number of substitutions possible from mono or represents no substitution; R, R', R Ａ’ , R Ｂ’ , R Ｃ’ , R Ｄ’ , R Ｅ’ , R Ｆ’ , and R Ｇ’ are each independently selected from the group consisting of hydrogen or deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof.

11. 2. The compound of claim 1, wherein the compound is selected from the group consisting of: 【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】 【Transformation 60】 【Chemistry 61】 【Transformation 62】 【Transformation 63】 【Chemistry 64】 【Transformation 65】

12. An organic light emitting device (OLED), comprising: an anode; a cathode; an organic layer disposed between the anode and the cathode; 10. An organic light emitting device (OLED) characterized in that the organic layer comprises the compound of claim 1.

13. 1. A consumer product comprising an organic light emitting device (OLED), the organic light emitting device (OLED) comprising: an anode; a cathode; an organic layer disposed between the anode and the cathode; 10. A consumer product characterized in that the organic layer comprises the compound of claim 1.

14. The compound is of formula (14), wherein R ＡＰ ~R ＡＳ or the compound of formula (2), wherein X9 to X16 are all C.

15. The compound is of formula (9), wherein R ５ The compound of claim 1 , wherein comprises a heteroaromatic group or a boryl group.

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