Organic electroluminescent materials and devices

Abstract

The present application relates to organic electroluminescent materials and devices. The present invention provides transition metal compounds having a 5-membered carbocyclic or heterocyclic ring in a unique configuration of fused rings according to Formula I: The compounds exhibit improved phosphorescent emission in the red to near IR region and can be used as emitter materials in organic electroluminescent devices.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 62 / 876,807, filed on July 22, 2019, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates generally to organometallic compounds and formulations and various uses thereof, including as emitters in devices such as organic light emitting diodes and related electronic devices. Background Art

[0004] Optoelectronic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many materials used to make the devices are relatively inexpensive, so organic optoelectronic devices have the potential to have cost advantages over inorganic devices. In addition, the inherent properties of organic materials (e.g., their flexibility) can make them more suitable for specific applications, such as manufacturing 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 can have performance advantages over conventional materials.

[0005] OLEDs utilize organic thin films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly attractive technology for use in applications such as flat panel displays, lighting, and backlighting.

[0006] One application of phosphorescent emitting molecules is full-color displays. Industry standards for such displays require pixels that are suitable for emitting specific colors (called "saturated" colors). Specifically, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, an absorption filter is used to filter the emission from a white backlight to produce red, green, and blue emissions. The same technology can also be used for OLEDs. White OLEDs can be single-emission layer (EML) devices or stacked structures. Color can be measured using CIE coordinates well known in the art. Summary of the invention

[0007] The present disclosure provides transition metal compounds having a 5-membered carbocyclic or heterocyclic ring in a unique configuration of a fused ring. The compounds exhibit improved phosphorescent emission in the red to near IR region and are suitable as emitter materials in organic electroluminescent devices.

[0008] In one aspect, the present disclosure provides a ligand L comprising Formula I A Mixed compounds

[0009]

[0010] Wherein: A is a 5-membered heterocyclic ring; Z 1 , Z 2 and Z 3 Each independently is C or N;

[0011] X 1 -X 7 are each independently C or N; the maximum number of N atoms in each ring B and ring C is two;

[0012] R A , R B and R C Each represents zero substitution, monosubstitution, or up to the maximum allowed substitution on its associated ring;

[0013] R A , R B and R C Each of the ligands L is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents may be joined or fused to form a ring; A Coordinated to metal M, as indicated by two dashed lines; metal M is coordinated to a different A and the ligand L A Other ligands may be linked to form tridentate, tetradentate, pentadentate or hexadentate ligands.

[0014] In another aspect, the present disclosure provides formulations of the compounds of the present disclosure.

[0015] In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound of the present disclosure.

[0016] In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a compound of the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 An organic light emitting device is shown.

[0018] Figure 2 An inverted organic light-emitting device without a separate electron transport layer is demonstrated. DETAILED DESCRIPTION

[0019] A. Terminology

[0020] Unless otherwise specified, the following terms used herein are defined as follows:

[0021] As used herein, the term "organic" includes polymeric materials and small molecule organic materials that can be used to make organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and a "small molecule" may actually be quite large. In some cases, a small molecule may include a repeating unit. For example, the use of a long chain alkyl group as a substituent does not remove a molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, for example as a side group on a polymer backbone or as part of a backbone. Small molecules can also serve as the core portion of a dendritic polymer, which consists of a series of chemical shells built on the core portion. The core portion of a dendritic polymer can be a fluorescent or phosphorescent small molecule emitter. A dendritic polymer can be a "small molecule", and all dendritic polymers currently used in the field of OLEDs are considered to be small molecules.

[0022] As used herein, "top" means farthest from the substrate, while "bottom" means closest to the substrate. Where a first layer is described as being "disposed "above" a second layer, the first layer is disposed farther from the substrate. Unless it is specified that the first layer is "in contact with" the second layer, there may be other layers between the first and second layers. For example, a cathode may be described as being "disposed "above" an anode even though various organic layers are present between the cathode and the anode.

[0023] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium in the form of a solution or suspension.

[0024] When a ligand is believed to directly contribute to the photosensitive property of an emissive material, the ligand may be referred to as "photosensitive." When a ligand is believed not to contribute to the photosensitive property of an emissive material, the ligand may be referred to as "ancillary," but the ancillary ligand may alter the properties of the photosensitive ligand.

[0025] As used herein, and as will be generally understood by one skilled in the art, a first "Highest Occupied Molecular Orbital" (HOMO) or "Lowest Unoccupied Molecular Orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum energy 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 energy 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 this diagram than a "lower" HOMO or LUMO energy level.

[0026] As used herein, and as one skilled in the art would generally understand, 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 typically measured as negative numbers relative to the 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 a downward direction. Thus, the definition of HOMO and LUMO energy levels follows different rules than work functions.

[0027] The terms "halo," "halogen," and "halo" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0028] The term "acyl" refers to a substituted carbonyl (C(O)-R s ).

[0029] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s OR-C(O)-OR s ) group.

[0030] The term "ether" refers to -OR s Group.

[0031] The terms "thio" or "thioether" are used interchangeably and refer to -SR s Group.

[0032] The term "sulfinyl" refers to -S(O)-R s Group.

[0033] The term "sulfonyl" refers to -SO2-R s Group.

[0034] The term "phosphino" refers to -P(R s )3 groups, wherein each R s Can be the same or different.

[0035] The term "silyl" refers to -Si(R s )3 groups, wherein each R s Can be the same or different.

[0036] The term "boryl" refers to -B(R s )2 group or its Lewis adduct -B(R s )3 groups, wherein R s Can be the same or different.

[0037] In each of the above, R s It may be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. s Selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0038] The term "alkyl" refers to and includes straight and branched chain alkyl groups. Preferred alkyl groups are those containing one to fifteen 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, 2,2-dimethylpropyl, etc. In addition, the alkyl group may be optionally substituted.

[0039] The term "cycloalkyl" refers to and includes monocyclic, polycyclic and spiroalkyl groups. Preferred cycloalkyl groups are cycloalkyl groups containing 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, etc. In addition, the cycloalkyl group may be optionally substituted.

[0040] The term "heteroalkyl" or "heterocycloalkyl" refers 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. In addition, the heteroalkyl or heterocycloalkyl group may be optionally substituted.

[0041] The term "alkenyl" refers to and includes straight and branched alkenyl groups. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group in which at least one carbon atom is 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 two to fifteen carbon atoms. In addition, alkenyl, cycloalkenyl or heteroalkenyl groups may be optionally substituted.

[0042] The term "alkynyl" refers to and includes straight and branched chain alkynyl groups. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are alkynyl groups containing two to fifteen carbon atoms. In addition, alkynyl groups may be optionally substituted.

[0043] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group. Additionally, the aralkyl group may be optionally substituted.

[0044] 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. Aromatic heterocyclic groups can be used interchangeably with heteroaryl. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom, and include cyclic amines, such as morpholinyl, piperidinyl, pyrrolidinyl, etc., and cyclic ethers / thioethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. In addition, heterocyclic groups can be optionally substituted.

[0045] The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. Polycyclic rings may have two or more rings in which two carbons are common to two adjacent rings (the rings are "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic and / or heteroaryl. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted.

[0046] The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. Heteroatoms include, but are not limited to, O, S, N, P, B, Si and Se. In many cases, O, S or N are preferred heteroatoms. Monocyclic heteroaromatic systems are preferably monocyclic rings with 5 or 6 ring atoms, and the rings may have one to six heteroatoms. Heteropolycyclic ring systems may have two or more rings in which two atoms are common to two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and / or heteroaryl. Heteropolycyclic aromatic ring systems may have one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryls are heteroaryls containing three to thirty carbon atoms, preferably three to twenty carbon atoms, and more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazole In some embodiments, the heteroaryl group is substituted with 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and aza analogs thereof. In some embodiments, the heteroaryl group is substituted with 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and aza analogs thereof. In some embodiments, the heteroaryl group is substituted with 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and aza analogs thereof. In some embodiments, the heteroaryl group is substituted with 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and aza analogs thereof. In some embodiments, the heteroaryl group is substituted with 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and aza analogs thereof.

[0047] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine and benzimidazole and their respective corresponding aza analogs are of particular interest.

[0048] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclyl, aryl and heteroaryl are independently unsubstituted or substituted with one or more typical substituents.

[0049] In many cases, the general substituent is selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.

[0050] In some cases, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, boryl, and combinations thereof.

[0051] In some cases, more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silanyl, boryl, aryl, heteroaryl, thio, and combinations thereof.

[0052] In other cases, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0053] The terms "substituted" and "substituted" refer to the bonding of substituents other than H to the relevant positions, such as carbon or nitrogen. For example, when R 1 When it represents a single substitution, one R 1 must not be H (i.e., substituted). Similarly, when R 1 When it indicates disubstituted, the two R 1 must not be H. Similarly, when R 1 When it indicates zero or no substitution, R 1 For example, it can be hydrogen with available valences for the ring atoms, such as the carbon atoms of benzene and the nitrogen atoms in pyrrole, or simply none for ring atoms with fully saturated valences, such as the nitrogen atoms in pyridine. The maximum number of substitutions possible in the ring structure will depend on the total number of available valences in the ring atoms.

[0054] As used herein, "combinations thereof" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that a person of ordinary skill in the art can envision from the applicable list. For example, alkyl and deuterium can be combined to form partially or fully deuterated alkyl; halogen and alkyl can be combined to form haloalkyl substituents; and halogen, alkyl and aryl can be combined to form haloaralkyl. In one example, the term substitution includes a combination of two to four listed groups. In another example, the term substitution includes a combination of two to three groups. In yet another example, the term substitution includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations including up to forty atoms that are not hydrogen or deuterium, or combinations including up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0055] The "aza" designation in the fragments described herein, i.e., aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the CH groups in the corresponding aromatic ring can be replaced by a nitrogen atom, for example and without any limitation, azatriphenylene encompasses dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed by the term as set forth herein.

[0056] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be easily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951 and U.S. Patent Application Publication No. US 2011 / 0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Review) 2007, 46, 7744-65 (which are incorporated by reference in their entirety) respectively describe the deuteration of methylene hydrogen in benzylamine and the effective way to replace aromatic ring hydrogen with deuterium.

[0057] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another part, its name can be written as if it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it is a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attaching fragments are considered equivalent.

[0058] In some cases, a pair of adjacent substituents can be optionally joined or fused to form a ring. Preferred rings are five, six or seven-membered carbocyclic or heterocyclic rings, including two cases where a portion of the ring formed by the pair of substituents is saturated and a portion of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that the two substituents involved can be immediately adjacent to each other on the same ring, or on two adjacent rings with two closest available substitutable positions (such as the 2, 2' positions in biphenyl or the 1, 8 positions in naphthalene), as long as they can form a stable fused ring system.

[0059] B. Compounds of the Disclosure

[0060] In one aspect, the present disclosure provides a ligand L comprising Formula I A Mixed compounds

[0061]

[0062] Wherein: A is a 5-membered heterocyclic ring; Z 1 , Z 2 and Z 3 Each independently is C or N;

[0063] X 1 -X 7 are each independently C or N; the maximum number of N atoms in each ring B and ring C is two;

[0064] R A , R B and R C Each represents zero substitution, monosubstitution, or up to the maximum allowed substitution on its associated ring;

[0065] R A , R B and R C Each of the ligands L is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents may be joined or fused to form a ring; A Coordinated to metal M, as indicated by two dashed lines; metal M is coordinated to a different A and the ligand L A Other ligands may be linked to form tridentate, tetradentate, pentadentate or hexadentate ligands.

[0066] In some embodiments of the compounds, R A , R B and R C Each of is independently hydrogen or a substituent selected from the group consisting of preferred general substituents defined herein.

[0067] In some embodiments, Z 1N and X 1 is C. In some embodiments, Z 1 C and X 1 is N. In some embodiments, Z 1 is N, and Z 2 and Z 3 is C. In some embodiments, Z 1 and Z 2 is N, and Z 3 is C. In some embodiments, Z 1 is C, and Z 2 and Z 3 is N.

[0068] In some embodiments, ring A is selected from the group consisting of: imidazole, triazole, oxazole, thiazole, pyrrole, azasilole, and N-heterocyclic carbene. In some embodiments, ring A is selected from the group consisting of:

[0069]

[0070] wherein: A is C or Si; R and R' are each independently selected from the group consisting of: alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof; and Z 4 and Z 5 Each is independently C or N, wherein the bond with a wavy line is a bond to ring B.

[0071] In some embodiments of the compounds, X 2 -X 7 Each is C.

[0072] In some embodiments, at least one R A Selected from the group consisting of hydrogen, deuterium, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof.

[0073] In some embodiments, an R B The substituent is an alkyl group or a cycloalkyl group.

[0074] In some embodiments, each R C The substituent is hydrogen. In some embodiments, two adjacent R C The substituents are joined together to form a 6-membered aromatic ring.

[0075] In some embodiments, two adjacent R A The substituents are joined together to form a 6-membered aromatic ring.

[0076] In some embodiments, an R A Substituent and an R BThe substituents are connected to form a ring. In some embodiments, the ring is a 5-membered, 6-membered or 7-membered ring. In some embodiments, the ring is further fused to form a polycondensed ring structure.

[0077] In some embodiments, M is selected from the group consisting of: Os, Ir, Pd, Pt, Cu, and Au. In some embodiments, M is Ir or Pt.

[0078] In some embodiments, the compound further comprises a substituted or unsubstituted acetylacetonate ligand.

[0079] In some embodiments, the ligand L A Select from the group consisting of:

[0080]

[0081]

[0082]

[0083] Where: R D represents zero substitution, single substitution, or up to the maximum allowed substitution on its associated ring; R D Z is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Z 6 -Z 9 are each independently C or N; and Z 6 -Z 9 At least two of them are C.

[0084] In some embodiments of the compound, the ligand L A Choose from L Ai-m A group consisting of, wherein m is an integer from 1 to 31, and when m is an integer from 1 to 15, i is an integer from 1 to 1800, and when m is an integer from 16 to 31, i is an integer from 1 to 540, wherein each L Ai-m Has the structure defined as follows:

[0085]

[0086]

[0087]

[0088]

[0089] For L Ai-m Each L Ai , when m is an integer from 1 to 15, R E and G are independently defined as follows:

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101] For L Ai-m Each L Ai , when m is an integer from 16 to 47, R E , R F and R G Each is independently defined as follows:

[0102]

[0103]

[0104]

[0105]

[0106]

[0107] Where R 1 To R 60 Has the following structure: and

[0108] Among them G 1 To G 30 Has the following structure:

[0109]

[0110] In some embodiments, the compound has the formula M(L A ) x (L B ) y (L C ) z , L A Optional for L A In any of the structures defined above, and L B and L C Each is a bidentate ligand; and wherein x is 1 or 2; y is 0, 1 or 2; z is 0, 1 or 2; and x+y+z is the oxidation state of the metal M.

[0111] In the case of a product having the formula M(L A ) x (L B ) y (L C ) z In some embodiments of the compound, the compound has a A )(L B )2、Ir(L A )2(L B )、Ir(L A )2(L C ) and Ir(L A )(L B )(L C ) composed of a group of formulas, where L A , L B and L C Different from each other.

[0112] In the case of a product having the formula M(L A ) x (L B ) y (L C ) z In some embodiments of the compound of the formula Pt(L A )(L B ), where L A and L B In some embodiments of the compound, L A and LB connected to form a tetradentate ligand.

[0113] In the case of a product having the formula M(L A ) x (L B ) y (L C ) z In some embodiments of the compound, L A Optional for L A In any of the structures defined above, and L B and L C Each independently selected from the group consisting of:

[0114]

[0115]

[0116] Where: Y 1 To Y 13 Each independently selected from the group consisting of carbon and nitrogen; Y' is selected from the group consisting of: BR e NR e , PR e ,O,S,Se,C=O,S=O,SO2,CR e R f 、SiR e R f and GeR e R f ; where R e and R f May be fused or joined to form a ring; R a , R b , R c and R d Each independently represents zero substitution, monosubstitution, or up to the maximum allowed substitution on its associated ring; each R a , R b , R c , R d , R e and R f is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and R a , R b , R c and R d Two adjacent substituents of may be fused or joined to form a ring or to form a multidentate ligand.

[0117] In the case of a product having the formula M(L A ) x (L B ) y (LC ) z In some embodiments of the compound, L A Optional for L A In any of the structures defined above, and L B and L C Each independently selected from the group consisting of:

[0118]

[0119]

[0120]

[0121] Where: R a '、R b ' and R c ' each independently represents zero substitution, monosubstitution or up to the maximum allowed substitution on its associated ring; R a , R b , R c , R N , R a '、R b ' and R c ' is independently hydrogen or a general substituent as described herein; and R a '、R b ' and R c Two adjacent substituents of ' may be fused or joined to form a ring or to form a multidentate ligand.

[0122] In the case of a material selected from Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )2(L C ) and Ir(L A )(L B )(L C In some embodiments of the compound of the formula consisting of the group consisting of A , L B and L C Different from each other, L A Optional for L A In any of the structures defined above, and L B Choose from L Bk A group consisting of, wherein k is an integer from 1 to 263 and L Bk Has the following structure:

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132] in:

[0133] L C For a structure-based The structure of L C1-I To L C768-I L Cj-I ;and

[0134] L Cj-II Based on structure The structure of L C1-II To L C768-II ,

[0135] For L Cj-I and L Cj-II Each L Cj , R 1 ' and R 2 'The definition is as follows:

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142] And R D1 To R D192 Has the following structure:

[0143]

[0144]

[0145]

[0146]

[0147] In the formula corresponding to Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )(L B )(L C ) or Ir(L A )2(L C ), L A and L C As defined above, and L B Selected from the group consisting of: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B124 , L B126 , L B128 , L B130 , L B32 , L B134 , L B136 , L B138 , L B140 , L B142 , L B144 , L B156 , L B58 , L B160 , L B162 , L B164 , L B168 , L B172 , L B175 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B222 , L B231 , L B233 , L B235 , L B237 , L B240 , L B242 , L B244 , L B246 , L B248 , LB250 , L B252 , L B254 , L B256 , L B258 , L B260 and L B262 .

[0148] In the formula corresponding to Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )(L B )(L C ) or Ir(L A )2(L C ), L A and L C As defined above, and L B Selected from the group consisting of: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , L B124 , L B126 , L B128 , L B132 , L B136 , L B138 , L B142 , L B156 , L B162 , L B204 , L B206 , L B214 , L B216 , L B218 , L B220 , L B231 , L B233 and L B237 .

[0149] In the formula corresponding to Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )(L B )(L C ) or Ir(L A )2(L C ), L A and L B As defined above, and LC Select from the group consisting of: only for R 1 ' and R 2 ' is defined as those L selected from the following structures Cj-I and L Cj-II : R D1 , R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D18 , R D20 , R D22 , R D37 , R D40 , R D41 , R D42 , R D43 , R D48 , R D49 , R D50 , R D54 , R D55 , R D58 , R D59 , R D78 , R D79 , R D81 , R D87 , R D88 , R D89 , R D93 , R D116 , R D117 , R D118 , R D119 , R D120 , R D133 , R D134 , R D135 , R D136 , R D143 , R D144 , R D145 , R D146 , R D147 , R D149 , R D151 , R D154 , R D155 , R D161 , R D175 and R D190 .

[0150] In the formula corresponding to Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )(L B )(L C) or Ir(L A )2(L C ), L A and L B As defined above, and L C Select from the group consisting of: R only 1' and R 2' L is defined as those selected from the following structures Cj-I and L Cj-II : R D1 , R D3 , R D4 , R D5 , R D9 , R D17 , R D22 , R D43 , R D50 , R D78 , R D116 , R D118 , R D133 , R D134 , R D135 , R D136 , R D143 , R D144 , R D145 , R D146 , R D149 , R D151 , R D154 , R D155 and R D190 .

[0151] In some embodiments of the compounds, the compound is selected from the group consisting of: corresponding to formula Ir(L A )(L B )2-Aimk, wherein L A Selected from the structure L as defined above Ai-m The group composed of L B Selected from the structure L as defined above Bk Groups formed;

[0152] Corresponding to the formula Ir(L A )2(L B )-A'-imk, wherein L A Selected from the structure L as defined above Ai-m The group composed of L B Selected from the structure L as defined above Bk Groups formed;

[0153] Corresponding to the formula Ir(L A )(L B )(LC )-BimkjI, wherein L A Selected from the structure L as defined above Ai-m The group composed of L B Selected from the structure L as defined above Bk The group composed of L C Selected from the structure L as defined above Cj-I Groups formed;

[0154] Corresponding to the formula Ir(L A )(L B )(L C )-B'-imkj-II, wherein L A Selected from the structure L as defined above Ai-m The group composed of L B Selected from the structure L as defined above Bk The group composed of L C Selected from the structure L as defined above Cj-II Groups formed;

[0155] Corresponding to each formula Ir(L A )2(L C )-CimjI, wherein L A Selected from the structure L as defined above Ai-m The group composed of L C Selected from the structure L as defined above Cj-I Groups formed; and

[0156] Corresponding to each formula Ir(L A )2(L C )-Cimj-II, wherein L A Selected from the structure L as defined above Ai-m The group composed of L C Selected from the structure L as defined above Cj-II Groups formed;

[0157] wherein i is an integer from 1 to 1808, m is an integer from 1 to 47, j is an integer from 1 to 768, and k is an integer from 1 to 263.

[0158] In the formula corresponding to Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )(L B )(L C ) or Ir(LA )2(L C ), L A and L B As defined above, and L C Select from the group consisting of:

[0159]

[0160]

[0161] In the case of a material selected from Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )2(L C ) and Ir(L A )(L B )(L C In some embodiments of the compound of the formula consisting of the group consisting of A , L B and L C Different from each other, the compounds are selected from the group consisting of:

[0162]

[0163]

[0164]

[0165]

[0166] C. OLEDs and Devices of the Present Disclosure

[0167] In another aspect, the present disclosure also provides an OLED device comprising a first organic layer containing a compound as disclosed in the above compound section of the present disclosure.

[0168] In some embodiments, the OLED comprises an anode, a cathode, and a first organic layer disposed between the anode and the cathode. The first organic layer may contain a ligand L comprising Formula I A Mixed compounds

[0169]

[0170] Wherein: A is a 5-membered heterocyclic ring; Z 1 , Z 2 and Z 3 Each independently is C or N;

[0171] X1 -X 7 are each independently C or N; the maximum number of N atoms in each ring B and ring C is two;

[0172] R A , R B and R C Each represents zero substitution, monosubstitution, or up to the maximum allowed substitution on its associated ring;

[0173] R A , R B and R C Each of the ligands L is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents may be joined or fused to form a ring; A Coordinated to metal M, as indicated by two dashed lines; metal M is coordinated to a different A and the ligand L A Other ligands may be linked to form tridentate, tetradentate, pentadentate or hexadentate ligands.

[0174] In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.

[0175] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene containing a benzo-fused thiophene or a benzo-fused furan, wherein any substituent in the host is a non-fused substituent independently selected from the group consisting of: C n H 2n+1 , OC n H 2n+1 、OAr1、N(C n H 2n+1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 、C≡CC n H 2n+1 、Ar1、Ar1-Ar2、C n H 2n -Ar1 or no substituent, wherein n is 1 to 10; and wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole and heteroaromatic analogs thereof.

[0176] In some embodiments, the organic layer may further include a host, wherein the host includes at least one chemical group selected from the group consisting of triphenylene, carbazole, indolecarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-borazinonaphtho[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolecarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene and aza-(5,9-dioxa-13b-borazinonaphtho[3,2,1-de]anthracene).

[0177] In some embodiments, the subject can be selected from the group of subjects consisting of:

[0178]

[0179] and combinations thereof.

[0180] In some embodiments, the organic layer may further include a host, wherein the host includes a metal complex.

[0181] In some embodiments, the compound as described herein may be a sensitizer; wherein the device may further comprise a receptor; and wherein the receptor may be selected from the group consisting of: a fluorescent emitter, a delayed fluorescent emitter, and combinations thereof.

[0182] In yet another aspect, an OLED of the present disclosure may further comprise an emissive region containing a compound as disclosed in the above compounds section of the present disclosure.

[0183] In some embodiments, the emission region may contain a ligand L comprising Formula I A Mixed compounds

[0184]

[0185] Wherein: A is a 5-membered heterocyclic ring; Z 1 , Z 2 and Z 3 Each independently is C or N;

[0186] X 1 -X 7 are each independently C or N; the maximum number of N atoms in each ring B and ring C is two;

[0187] R A , R B and R C Each represents zero substitution, monosubstitution, or up to the maximum allowed substitution on its associated ring;

[0188] RA , R B and R C Each of the ligands L is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents may be joined or fused to form a ring; A Coordinated to metal M, as indicated by two dashed lines; metal M is coordinated to a different A and the ligand L A Other ligands may be linked to form tridentate, tetradentate, pentadentate or hexadentate ligands.

[0189] In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED), the organic light-emitting device having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compound section of the present disclosure.

[0190] In some embodiments, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may contain a ligand L comprising Formula I A Mixed compounds

[0191]

[0192] Wherein: A is a 5-membered heterocyclic ring; Z 1 , Z 2 and Z 3 Each independently is C or N;

[0193] X 1 -X 7 are each independently C or N; the maximum number of N atoms in each ring B and ring C is two;

[0194] R A , R B and R C Each represents zero substitution, monosubstitution, or up to the maximum allowed substitution on its associated ring;

[0195] R A , R B and R C Each of the ligands L is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents may be joined or fused to form a ring; A Coordinated to metal M, as indicated by two dashed lines; metal M is coordinated to a different A and the ligand L A Other ligands may be linked to form tridentate, tetradentate, pentadentate or hexadentate ligands.

[0196] In some embodiments, the consumer product can be one of the following: a flat panel display, a computer monitor, a medical monitor, a television, a sign, a light for interior or exterior lighting and / or signaling, a head-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cellular telephone, a tablet computer, a tablet phone, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay having a diagonal of less than 2 inches, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.

[0197] In general, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When an electric current is applied, the anode injects holes and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When electrons and holes are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. When the exciton relaxes through a light emission mechanism, light is emitted. In some cases, the exciton can be localized on an excimer or an excited complex. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0198] Several OLED materials and configurations are described in US Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

[0199] The first OLEDs used emissive molecules that emitted light from a singlet state ("fluorescence"), as disclosed, for example, in US Pat. 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.

[0200] Recently, OLEDs with emissive materials that emit light from triplet states ("phosphorescence") have been demonstrated. Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices", Nature, Vol. 395, 151-154, 1998 ("Baldo-I"); and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence", Appl. Phys. Lett., Vol. 75, Nos. 3, 4-6 (1999) ("Baldo-II"), which are incorporated by reference in their entirety. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704, Columns 5-6, which is incorporated by reference.

[0201] Figure 1 An organic light-emitting device 100 is shown. The figure is not necessarily drawn to scale. The 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 emission 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 blocking layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 can be manufactured by depositing the layers in sequence. The properties and functions of these various layers and example materials are described in more detail in US 7,279,704, columns 6-10, which are incorporated by reference.

[0202] More examples of each of these layers are available. 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 transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of luminescent 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 transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes comprising a composite cathode having a thin layer of a metal (e.g., Mg:Ag) with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use of barrier 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 entirety. 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.

[0203] Figure 2 An inverted OLED 200 is shown. 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 manufactured by depositing the layers in order. Because the most common OLED configuration has a 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 can be used in the corresponding layers of device 200. Figure 2 An example is provided of how some layers may be omitted from the structure of device 100 .

[0204] Figure 1 and 2The simple layered structures described in are provided by way of non-limiting examples, and it should be understood that embodiments of the present disclosure may be used in conjunction with various other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be obtained by combining the various layers described in different ways, or the layers may be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than the specifically described materials may be used. Although many of the examples provided herein describe the various layers as comprising a single material, it should be understood that a combination of materials may be used, such as a mixture of a host and a dopant, or more generally, a mixture. In addition, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, the OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise, for example, Figure 1 and 2 Multiple layers of said different organic materials.

[0205] Structures and materials not specifically described may also be used, such as OLEDs containing polymeric materials (PLEDs), such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of another example, an OLED having a single organic layer may be used. OLEDs may be stacked, such 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 Figure 1 and 2 For example, the substrate may include angled reflective surfaces to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and / or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0206] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet (as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, incorporated by reference in their entirety), organic vapor phase deposition (OVPD) (as described in U.S. Pat. No. 6,337,102 to Forrest et al., incorporated by reference in their entirety), and deposition by organic vapor jet printing (OVJP) (as described in U.S. Pat. No. 7,431,968, incorporated by reference in their entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding (as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety), and patterning associated with some of the 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 make it compatible with a specific deposition method. For example, branched or unbranched substituents such as alkyl and aryl groups, preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 or more carbons may be used, and 3 to 20 carbons are a preferred range. Materials having asymmetric structures may have better solution processability than materials having symmetric structures because asymmetric materials may have a lower tendency to recrystallize. Dendritic polymer substituents may be used to enhance the ability of small molecules to withstand solution processing.

[0207] The device manufactured according to the embodiment of the present disclosure may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrode and the organic layer from exposure to harmful substances in an environment including moisture, steam and / or gas. The barrier layer can be deposited on a substrate, an electrode, under a substrate, an electrode, or beside a substrate, an electrode, or on any other part (including an edge) of the device. 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 a composition having a single phase and a composition having multiple phases. Any suitable material or material combination may be used for the barrier layer. The barrier layer may be combined with an inorganic compound or an organic compound or both. A preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material, as described in U.S. Patent No. 7,968,146, PCT Patent Application No. PCT / US2007 / 023098, and No. PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. In order to be considered a "mixture", the aforementioned polymeric material and non-polymeric material constituting the barrier layer should be deposited under the same reaction conditions and / or deposited simultaneously. The weight ratio of polymeric material to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and non-polymeric material may be produced from the same precursor material. In one example, the mixture of polymeric material and non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

[0208] The device manufactured according to the embodiment of the present disclosure can be incorporated into a variety of electronic component modules (or units), which can be incorporated into a variety of electronic products or intermediate components. Examples of the electronic products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels), etc. that can be used by end-user product manufacturers. The electronic component module may optionally include driving electronic devices and / or power supplies. The device manufactured according to the embodiment of the present disclosure can be incorporated into a variety of consumer products, and the consumer product has one or more electronic component modules (or units) incorporated therein. A consumer product comprising an OLED is disclosed, and the OLED includes a compound of the present disclosure in an organic layer in the OLED. The consumer product should include any kind of product containing one or more of one or more light sources and / or a certain type of visual display. Some examples of consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior lighting and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, phones, cellular phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, light therapy devices, and signage. Various control mechanisms can be used to control devices manufactured according to the present disclosure, including passive matrices and active matrices. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as 18°C ​​to 30°C, and more preferably at room temperature (20-25°C), but can be used outside this temperature range (e.g., -40°C to 80°C).

[0209] More details regarding OLEDs and the definitions set forth above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0210] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can employ the materials and structures. More generally, organic devices such as organic transistors can employ the materials and structures.

[0211] In some embodiments, the OLED has one or more features 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.

[0212] In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises an RGB pixel arrangement or a white plus color filter pixel arrangement. 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.

[0213] In some embodiments, the compound can be an emitting dopant. In some embodiments, the compound can be emitted via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also referred to as E-type delayed fluorescence, see, for example, U.S. Application No. 15 / 700,352, which is incorporated herein by reference in its entirety), triplet-triplet elimination, or a combination of these processes. In some embodiments, the emitting dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homogeneous (each ligand is the same). In some embodiments, the compound can be mixed (at least one ligand is different from the others). In some embodiments, when there is more than one ligand coordinated to the metal, the ligand can be all the same. In some other embodiments, at least one ligand is different from other ligands. In some embodiments, each ligand can be different from each other. This is also true in the embodiments where the ligand coordinated to the metal can be connected to other ligands coordinated to the metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligand. Thus, where coordinating ligands are linked together, in some embodiments all of the ligands may be identical, and in some other embodiments at least one of the linked ligands may be different from the other ligand(s).

[0214] In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED, wherein one or more layers in the OLED contain an acceptor in the form of one or more fluorescent and / or delayed fluorescent emitters. In some embodiments, the compound can be used as a component of an excited complex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to the acceptor and the acceptor will emit energy or further transfer energy to the final emitter. The acceptor concentration can be in the range of 0.001% to 100%. The acceptor can be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can be generated by any one or all of the sensitizer, the acceptor, and the final emitter.

[0215] According to another aspect, a formulation comprising a compound described herein is also disclosed.

[0216] The OLEDs disclosed herein may be incorporated into one or more of consumer products, electronic component modules, and lighting panels.The organic layer may be an emissive layer, and the compound may be an emissive dopant in some embodiments, while the compound may be a non-emissive dopant in other embodiments.

[0217] In another aspect of the present invention, a formulation comprising the novel compounds disclosed herein is described. The formulation may include one or more components disclosed herein 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.

[0218] The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure or their monovalent or multivalent variants. In other words, the compounds of the present invention or their monovalent or multivalent variants 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 referred to as supramolecules). As used herein, a "monovalent variant of a compound" refers to a portion that is identical to the compound but one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a "multivalent variant of a compound" refers to a portion that is identical to the compound but more than one hydrogen has been removed and replaced with one or more bonds to the rest of the chemical structure. In the case of a supramolecule, the compounds of the present invention can also be incorporated into a supramolecular complex without covalent bonds.

[0219] D. Combinations of Compounds of the Disclosure with Other Materials

[0220] The materials described herein as being suitable for use in a particular layer in an organic light-emitting device can be used in combination with a variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in combination with a wide variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0221] a) Conductive dopants:

[0222] The charge transport layer can be doped with a conductivity dopant to substantially change its charge carrier density, which in turn will change its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductivity dopant, and an n-type conductivity dopant is used in the electron transport layer.

[0223] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with references disclosing those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.

[0224]

[0225] b)HIL / HTL:

[0226] The hole injection / transport material used in the present disclosure is not particularly limited, and any compound can be used as long as the compound is generally used as a hole injection / transport material. Examples of the material include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolecarbazole derivatives; polymers containing fluorocarbons; polymers having a conductive dopant; conductive polymers such as PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x; p-type semiconductive organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes; and crosslinkable compounds.

[0227] Examples of aromatic amine derivatives for use in HIL or HTL include, but are not limited to, the following general structure:

[0228]

[0229] Ar 1 To Ar 9 Each of the following is selected from the group consisting of aromatic hydrocarbon cyclic compounds: benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline , quinoxaline, naphthridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units, wherein the cyclic structural units are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are bonded to each other directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. Each Ar may be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0230] In one aspect, Ar 1 To Ar 9 Independently selected from the group consisting of:

[0231]

[0232] Wherein k is an integer from 1 to 20; X 101 To X 108 is C (including CH) or N; Z 101 It is NAr 1, O or S; Ar 1 Having the same groups as defined above.

[0233] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0234]

[0235] Where Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 is independently selected from C, N, O, P and S; L 101 is an auxiliary ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0236] In one aspect, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. In another aspect, (Y 101 -Y 102 ) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os and Zn. In another aspect, the metal complex has a relative + / Fc coupling has a minimum oxidation potential in solution of less than about 0.6 V.

[0237] 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 disclosing those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, J P2007091719, JP2008021687, JP2014-009196, KR20110088898, KR2013007 7473, TW201139402, US06517957, US20020158242, US20030162053, US2005 0123751, US20060182993, US20060240279, US20070145888, US2007018187 4. US20070278938, US20080014464, US20080091025, US20080106190, US200 80124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US201 1007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO0 5075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO201 3087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO 2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921,WO2014034791, WO2014104514, WO2014157018. ,

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245] c) EBL:

[0246] 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 produce substantially higher efficiency and / or longer lifetime than a similar device lacking a blocking layer. In addition, a blocking layer can be used to confine emission to desired areas of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as used in one of the hosts described below.

[0247] d) Subject:

[0248] The light-emitting layer of the organic EL device of the present disclosure 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. Examples of host materials are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than the triplet energy of the dopant. Any host material may be used with any dopant as long as the triplet criterion is satisfied.

[0249] Examples of metal complexes used as hosts preferably have the following general formula:

[0250]

[0251] Where Met is a metal; (Y 103 -Y 104) is a bidentate ligand, Y 103 and Y 104 is independently selected from C, N, O, P and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0252] In one aspect, the metal complex is:

[0253]

[0254] where (ON) is a bidentate ligand with a metal coordinated to O and N atoms.

[0255] In another aspect, Met is selected from Ir and Pt. In another aspect, (Y 103 -Y 104 ) is a carbene ligand.

[0256] In one aspect, the host compound contains at least one selected from the following group: a group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline , quinoxaline, naphthridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units, wherein the cyclic structural units are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are bonded to each other directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. Each option in each group may be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0257] In one aspect, the subject compound contains at least one of the following groups in the molecule:

[0258]

[0259]

[0260] Where R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino and combinations thereof, and when it is aryl or heteroaryl, it has the same definition as Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20. X 101 To X 108 Z is independently selected from C (including CH) or N. 101 and Z 102 Independently selected from NR 101 , O or S.

[0261] 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 disclosing those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US2009 0017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, U S20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO200 6114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO20090 86028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133 649. WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, US9466803,

[0262]

[0263]

[0264]

[0265]

[0266]

[0267] e) Other emitters:

[0268] One or more other emitter dopants may be used in combination with the compounds of the present invention. Examples of other emitter dopants are not particularly limited, and any compound may be used as long as the compound is commonly used as an emitter material. Examples of suitable emitter materials include, but are not limited to, compounds that can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0269] 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 disclosing those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP201310263, JP4478555, KR1020090133652, KR20120090133653. 32054, KR20130043460, TW201332980, US06699599, US06916554, US200100 19782, US20020034656, US20030068526, US20030072964, US20030138657, U U.S. 20060202194, US20060251923, US20070034863, US20070087321, US200701 03060, US20070111026, US20070190359, US20070231600, US2007034863, US 2007104979, US2007104980, US2007138437, US2007224450, US2007278936 , US20080020237, US20080233410, US20080261076, US20080297033, US2008 05851, US2008161567, US2008210930, US20090039776, US20090108737, US 20090115322, US20090179555, US2009085476, US2009104472, US201000905 91. US20100148663, US20100244004, US20100295032, US2010102716, US20 10105902, US2010244004, US2010270916, US20110057559, US20110108822,US20110204333、US2011215710、US2011227049、US2011285275、US2012292601、US20130146848、US2013033172、US2013165653、US2013181190、US2013334521、US20140246656、US2014103305、US6303238、US6413656、US6653654、US6670645、US6687266、US6835469、US6921915、US7279704、US7332232、US7378162、US7534505、US7675228、US7728137、US7740957、US7759489、US7951947、US8067099、US8592586、US8871361、WO06081973、WO06121811、WO07018067、WO07108362、WO07115970、WO07115981、WO08035571、WO2002015645、WO2003040257、WO2005019373、WO2006056418、WO2008054584、WO2008078800、WO2008096609、WO2008101842、WO2009000673、WO2009050281、WO2009100991、WO2010028151、WO2010054731、WO2010086089、WO2010118029、WO2011044988、WO2011051404、WO2011107491、WO2012020327、WO2012163471、WO2013094620、WO2013107487、WO2013174471、WO2014007565、WO2014008982、WO2014023377、WO2014024131、WO2014031977、WO2014038456、WO2014112450。、

[0270]

[0271]

[0272]

[0273]

[0274]

[0275] f)HBL:

[0276] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime than a similar device lacking a blocking layer. In addition, a blocking layer can be used to confine emission to a desired area of ​​the 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.

[0277] In one aspect, the compounds used in HBL contain the same molecules or the same functional groups as used in the subjects described above.

[0278] In another aspect, the compound used in HBL contains at least one of the following groups in the molecule:

[0279]

[0280] wherein k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0281] g)ETL:

[0282] 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 may be used as long as it is generally used to transport electrons.

[0283] In one aspect, the compound used in the ETL contains at least one of the following groups in the molecule:

[0284]

[0285] Where R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino and combinations thereof, and when it is aryl or heteroaryl, it has a similar definition to Ar above. Ar1 To Ar 3 has a similar definition to Ar mentioned above. k is an integer from 1 to 20. 101 To X 108 is selected from C (including CH) or N.

[0286] In another aspect, the metal complex used in the ETL contains (but is not limited to) the following general formula:

[0287]

[0288] wherein (ON) or (NN) is a bidentate ligand having a metal coordinated to atoms O, N or N, N; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

[0289] 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 disclosing those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, and US2009018957. 10108990, US2011156017, US2011210320, US2012193612, US2012214993, US201401 4925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO20 07111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO201110 5373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

[0290]

[0291]

[0292]

[0293] h) Charge Generation Layer (CGL)

[0294] In a tandem or stacked OLED, the CGL plays a fundamental role in the performance and consists of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied by the CGL and electrodes. The electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; then, the bipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductivity dopants used in the transport layer.

[0295] In any of the above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any specific listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, etc., may be in their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (such as (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) may also be in their non-deuterated, partially deuterated, and fully deuterated forms.

[0296] It should be understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the present invention. For example, other materials and structures may be used to replace many materials and structures described herein without departing from the spirit of the present invention. The present invention as required may therefore include variations of specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that the various theories about why the present invention works are not intended to be restrictive.

[0297] E. Experimental Data

[0298]

[0299] A solution of 2-(4-(tert-butyl)naphthalen-2-yl)-1-(2,6-dimethylphenyl)-1H-benzo[d]imidazole (1.303 g, 3.22 mmol, 2.0 equiv) was bubbled with nitrogen for 10 minutes. Iridium(III) chloride hydrate (0.51 g, 1.611 mmol) was added and the reaction mixture was heated at 100 °C overnight. The reaction mixture was cooled to room temperature and diluted with methanol solution. 3,7-diethylnonane-4,6-dione (0.684 g, 3.22 mmol, 2.0 equiv) and powdered potassium carbonate (0.668 g, 4.83 mmol, 3.0 equiv) were added and the reaction mixture was stirred at 40 °C for 3 hours. Water (10 mL) was added to the cooled mixture. The solid was filtered and washed with water (2×3 mL) followed by methanol (3×1 mL). The orange solid was purified on an Interchim automated system (80 g silica column) eluting with a gradient of 0-20% dichloromethane / heptane. The recovered material was triturated with 10% dichloromethane / methanol (approximately 10 mL) to give an orange solid (1.55 g, 98.9% UPLC purity).

[0300]

[0301] A solution of 1-(2,6-dimethylphenyl)-2-(naphthalen-2-yl)-1H-benzo[d]imidazole (2.0 g, 5.9 mmol, 2.1 equiv) in diethylene glycol dimethyl ether (19.5 mL) and deionized ultrafiltered (DIUF) water (6.5 mL) was bubbled with nitrogen for 25 minutes. Iridium(III) chloride hydrate (1.0 g, 2.79 mmol, 1.0 equiv) was added and the reaction mixture was heated at 102°C. After 20 hours, the reaction mixture was cooled to 45°C and then filtered. The solid was washed with methanol (3×20 mL) and then air-dried to give the presumed diμ-chloro-tetrakis-[(3-(2,6-dimethylphenyl)-2-(naphthalen-2-yl)-3′-yl)-1H-benzo[d]imidazol-1-yl]diiridium(III) (1.15 g, 46% yield) as a light orange solid.

[0302] 3,7-Diethylnonane-4,6-dione (380 mg, 1.8 mmol, 3.0 equiv) was added to a solution of diμ-chloro-tetrakis-[(3-(2,6-dimethylphenyl)-2-(naphthalen-2-yl)-3'-yl)-1H-benzo[d]imidazol-1-yl]diiridium(III) (1.1 g, 0.596 mmol, 1.0 equiv) in 2-ethoxyethanol (15 mL), and the reaction mixture was bubbled with nitrogen for 5 minutes. Powdered potassium carbonate (330 mg, 2.4 mmol, 4.0 equiv) was added, and the reaction mixture was stirred at 50 °C in a flask covered with foil to block light for 24 hours. DIUF water (15 mL) was added to the cooled reaction mixture and the slurry was stirred for 30 minutes. The suspension was filtered, the solids washed with DIUF water (3 x 5 mL) and methanol (3 x 10 mL), then air dried. The resulting red solid (1.3 g) was dissolved in dichloromethane (15 mL) and chromatographed on silica gel (50 g) coated with basic alumina (10 g) eluting with 100% dichloromethane to afford bis[(3-(2,6-dimethylphenyl)-2-(naphthalen-2-yl)-3'-yl)-1H-benzo[d]imidazol-1-yl]-(3,7-diethyl-4,6-nonanedione-k2O,O')iridium(III) (1.08 g, 82% yield, 99.6% UPLC purity).

[0303]

[0304] A solution of 1-(2,6-dimethylphenyl)-2-(naphthalen-1-yl)-1H-benzo[d]imidazole (2.0 g, 5.9 mmol, 2.1 equiv) in diethylene glycol dimethyl ether (19.5 mL) and DIUF water (6.5 mL) was bubbled with nitrogen for 25 minutes. Iridium(III) chloride hydrate (1.0 g, 2.79 mmol, 1.0 equiv) was added and the reaction mixture was heated at 102°C. After 20 hours, the reaction mixture was cooled to 45°C and filtered. The resulting solid was washed with methanol (3×20 mL) and then air-dried to give di-μ-chloro-tetrakis[(3-(2,6-dimethylphenyl)-2-(naphthalen-1-yl)-2′-yl)-1H-benzo[d]imidazole-1-yl]diiridium(III) (2.0 g, 80% yield) as a dark orange solid.

[0305] 3,7-Diethylnonane-4,6-dione (690 mg, 3.25 mmol, 3.0 equiv) was added to a solution of di-μ-chloro-tetrakis[(3-(2,6-dimethylphenyl)-2-(naphthalen-1-yl)-2'-yl)-1H-benzo[d]imidazol-1-yl]diiridium(III) (2 g, 1.08 mmol, 1.0 equiv) in 2-ethoxyethanol (25 mL), and the reaction mixture was bubbled with nitrogen for 5 minutes. Powdered potassium carbonate (599 mg, 4.34 mmol, 4.0 equiv) was added, and the reaction mixture was stirred at 50 °C in a flask covered with foil to block light for 2 hours. DIUF water (25 mL) was added to the cooled reaction mixture and the slurry was stirred for 30 minutes. The suspension was filtered, and the resulting solid was washed with DIUF water (3×10 mL) and methanol (3×15 mL), then air-dried. The orange solid (2.2 g) was dissolved in dichloromethane (20 mL) and dry loaded onto celite. The absorbed material was chromatographed on silica gel (100 g) coated with basic alumina (20 g), eluting with 50% dichloromethane / hexanes to give bis[(3-(2,6-dimethylphenyl)-2-(naphthalen-1-yl)-2'-yl)-1H-benzo[d]imidazol-1-yl]-(3,7-diethyl-4,6-nonanedione-k2O,O')iridium(III) (1.5 g, 62% yield, 99.6% UPLC purity).

[0306] Device Examples

[0307] All devices are operated under high vacuum (<10 -7 The anode electrode was 80 nm of indium tin oxide (ITO). The cathode electrode consisted of 1 nm of LiQ followed by 100 nm of Al. Immediately after fabrication, all devices were encapsulated with epoxy-sealed glass lids in a nitrogen glove box (<1 ppm of H2O and O2), and a moisture absorber was incorporated inside the package.

[0308] Starting from the ITO surface, the organic stack of the device example is composed of the following in sequence: 10 nm of LG-101 (purchased from LG Chem. Inc.) as a hole injection layer (HIL); 45 nm of PPh-TPD as a hole transport layer (HTL); 40 nm of an emissive layer (EML), which is composed of a premixed host doped with 3 wt% of a compound of the present invention or a comparative compound as an emitter; 35 nm of aDBT-ADN with 35 wt% LiQ as an electron transport layer (ETL). The premixed host is composed of a mixture of HM2 (18 wt%) in HM1 and is deposited from a single evaporation source. The chemical structures of the compounds used are shown below:

[0309]

[0310]

[0311] A summary of the device data, including the emission λ, is provided in Table 1 below. max , FWHM, voltage, luminous efficiency (LE), external quantum efficiency (EQE), and power efficiency (PE) (recorded at 1000 nits for device examples). The results are reported in the form normalized to the Comparative Example 2 device.

[0312] Table 1

[0313]

[0314] The data in Table 1 show that the device using the present invention example as an emitter exhibits red emission with a narrower emission spectrum (FWHM = 68 nm) compared to Comparative Example 1 (FWHM = 86 nm) and Comparative Example 2 (FWHM = 84 nm). In addition, the device using the present invention example achieves lower voltage, higher luminous efficiency, power efficiency, and EQE compared to the comparative example. The only difference between the present invention example compound and the comparative example compound is the structure of the naphthyl group. The results show that the present invention compound can be used as an emitter in an organic electroluminescent device to improve performance.

Claims

1. A compound having the formula Ir(L A )2(L C ) 1 mixed compound, Ligand L A for: L C for in: X 1 is C; and X 2 -X 7 Each independently is C or N; The maximum number of N atoms in each ring B and ring C is two; R B , R C and R D Each represents zero substitution, monosubstitution, or up to the maximum allowed substitution on its associated ring; R B , R C and R D Each of the is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, amino, silane, alkenyl, aryl, nitrile, and combinations thereof; R is selected from the group consisting of: alkyl, cycloalkyl, aryl, and combinations thereof; Z 6 -Z 9 are each independently C or N; and Z 6 -Z 9 At least two of them are C; The ligand L A is coordinated to Ir, as indicated by the two dashed lines; and Each R a , R b and R c is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, amino, silanyl, alkenyl, aryl, heteroaryl, nitrile, and combinations thereof.

2. The compound according to claim 1, wherein the ligand L A Choose from L Ai-m 355 to 363, 365 to 373, 375 to 383, 385 to 393, 405 to 413, 415 to 433, 425 to 443, 435 to 453, 445 to 463, 465 to 473, 485 to 503, 485 to 513, 485 to 523, 485 to 534, 485 to 543, 490 to 613, 500 to 623, 510 to 635, 511 to 636, 512 to 637, 513 to 638, 514 to 639, 525 to 643, 526 to 653, 527 to 663, 528 to 673, 529 to 683 373, 375 to 383, 385 to 393, 395 to 403, 405 to 413, 415 to 423, 425 to 433, 435 to 443, 445 to 453, 455 to 463, 465 to 473, 475 to 483, 485 to 493, 495 to 503, 505 to 513, 515 to 523 , 525 to 533, 535 to 540, 841 to 843, 845 to 853, 855 to 863, 865 to 870, 901 to 903, 905 to 913, 915 to 923, 925 to 930, 1111 to 1113, 1115 to 1123, 1125 to 1133, 1135 to 1143, 114 5 to 1153, 1155 to 1163, 1165 to 1173, 1175 to 1183, 1185 to 1193, 1195 to 1203, 1205 to 1213, 1215 to 1223, 1225 to 1233, 1235 to 1243, 1245 to 1253, 1255 to 1263, 1265 to 1 273、1275 to 1283、1285 to 1293、1295 to 1303、1305 to 1313、1315 to 1323、1325 to 1333、1335 to 1343、1345 to 1353、1355 to 1363、1365 to 1373、1375 to 1383、1385 to 1393、 1395 to 1403, 1405 to 1413, 1415 to 1423, 1425 to 1433, 1435 to 1443, 1445 to 1453, 1455 to 1463, 1465 to 1470, 1651 to 1653, 1655 to 1663, 1665 to 1673, 1675 to 1683, 1685 from 1703 to 1713, from 1715 to 1723, from 1725 to 1733, from 1735 to 1743, from 1745 to 1753, from 1755 to 1763, from 1765 to 1773, from 1775 to 1783, from 1785 to 1793 and from 1801 to 1808, wherein each L Ai-m Has the structure defined below: For L Ai-m Each L Ai , when m is 2 or 3, R E and G are independently defined as follows: Where R 2 To R 4 , R 6 To R 9 , R 11 To R 18 , R 29 , R 31 , R 38 To R 49 and R 56 To R 60 Has the following structure: and Among them G 1 To G 3 , G 5 To G 13 , G 15 To G 23 and G 25 To G 32 Has the following structure:

3. The compound according to claim 2, wherein the compound is selected from the group consisting of: Corresponding to each formula Ir(L A )2(L C )-CimjI, wherein L A For L Ai-m And L C For L Cj-I ; Corresponding to each formula Ir(L A )2(L C )-Cimj-II, wherein L A For L Ai-m And L C For L Cj-II ; wherein when m is 2 or 3, i is 31 to 33, 35 to 43, 45 to 53, 55 to 63, 65 to 73, 75 to 83, 85 to 93, 95 to 103, 105 to 113, 115 to 120, 151 to 153, 155 to 163, 165 to 173, 175 to 183, 185 to 193, 195 to 203, 205 to 213, 215 to 223, 225 to 233, 235 to 243, 245 to 253, 255 to 263, 265 to 270, 301 to 303, 305 to 313, 315 to 323, 325 to 333, 335 to 343, 345 to 353, 355 to 363, 365 to 373, 375 to 383, 385 to 393, 395 to 403, 405 to 413, 415 to 423, 425 to 433, 435 to 443, 445 to 453, 455 to 463, 465 to 473, 475 to 483, 485 to 493, 495 to 503, 505 to 513, 515 to 523, 525 to 533 5 to 533, 535 to 540, 841 to 843, 845 to 853, 855 to 863, 865 to 870, 901 to 903, 905 to 913, 915 to 923, 925 to 930, 1111 to 1113, 1115 to 1123, 1125 to 1133, 1135 to 1143, 1145 to 1153, 1155 to 1163, 1165 to 1173, 1175 to 1183, 1185 to 1193, 1195 to 1203, 1205 to 1213, 1215 to 1223, 1225 to 1233, 1235 to 1243, 1245 to 1253, 1255 to 1263, 1265 to 12 73, 1275 to 1283, 1285 to 1293, 1295 to 1303, 1305 to 1313, 1315 to 1323, 1325 to 1333, 1335 to 1343, 1345 to 1353, 1355 to 1363, 1365 to 1373, 1375 to 1383, 1385 to 1393, integers from 1395 to 1403, 1405 to 1413, 1415 to 1423, 1425 to 1433, 1435 to 1443, 1445 to 1453, 1455 to 1463, 1465 to 1470, 1651 to 1653, 1655 to 1663, 1665 to 1673, 1675 to 1683, 1685 to 1693, 1695 to 1703, 1705 to 1713, 1715 to 1723, 1725 to 1733, 1735 to 1743, 1745 to 1753, 1755 to 1763, 1765 to 1773, 1775 to 1783, 1785 to 1793, and 1801 to 1808, wherein L Cj-I Based on structure The structure of L C1-I To L C768-I ;and L Cj-II Based on structure The structure of L C1-II To L C768-II , For L Cj-I and L Cj-II Each L Cj , R 1 ' and R 2 'The definition is as follows: And R D1 To R D192 Has the following structure:

4. A mixed compound, wherein the compound is:

5. An organic light emitting device (OLED), comprising: anode; cathode; and An organic layer disposed between the anode and the cathode, wherein the organic layer contains the mixed compound according to any one of claims 1-4.

6. The OLED of claim 5, wherein the organic layer further comprises a host, wherein the host comprises at least one chemical moiety selected from the group consisting of naphthalene, fluorene, triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-naphthalene, aza-fluorene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

7. The OLED according to claim 6, wherein the host is selected from the group consisting of: and combinations thereof.

8. A consumer product comprising an organic light emitting device (OLED), wherein the OLED comprises: anode; cathode; and An organic layer disposed between the anode and the cathode, wherein the organic layer contains the mixed compound according to any one of claims 1-4.

9. A formulation comprising a compound according to any one of claims 1-4.

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