Organic electroluminescent materials and devices

Abstract

This application relates to organic electroluminescent materials and devices. The present invention provides transition metal compounds with 1,2,3-triazine. Also provided are formulations containing these transition metal compounds with 1,2,3-triazine. Also provided are OLEDs and related consumer products utilizing these transition metal compounds with 1,2,3-triazine.

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. 63 / 013,930, filed on April 22, 2020, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure generally relates 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] For various reasons, optoelectronic devices utilizing organic materials are becoming increasingly popular. Many of the materials used to manufacture the devices are relatively inexpensive, so organic optoelectronic devices have the potential to offer 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 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, absorption filters are 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, which are well known in the art. Summary of the Invention

[0007] In one aspect, the present disclosure provides a ligand L comprising formula I A Compounds:

[0008]

[0009] in,

[0010] A 1 and A 2each independently a monocyclic or polycyclic fused ring system comprising one or more fused or non-fused 5- or 6-membered carbocyclic or heterocyclic rings;

[0011] X 1 -X 4 are independently C or N, with the proviso that X 1 -X 4 At least one of them is C and X 1 -X 4 At least one of them is N;

[0012] K 1 and K 2 are each independently selected from the group consisting of: a direct bond, O, and S;

[0013] L 1 selected from the group consisting of a single bond, O, S, C═R′, CR′R″, SiR′R″, GeRR′, BR′, BR′R″, and NR′;

[0014] R A and R D Each represents zero substitution, monosubstitution, or up to the maximum allowable substitution on its associated ring;

[0015] R A and R D At least one of them has a structure of formula II, which is the same as the corresponding A 1 and A 2 condensed;

[0016]

[0017] Z 1 -Z 4 Each independently selected from the group consisting of: CRR', SiRR' and GeRR', with the proviso that Z 1 -Z 4 At least one of them is GeRR' or SiRR';

[0018] n = 0 or 1;

[0019] When n is 1 and A 1 or A 2 When Z is a pyridine ring fused to Formula II, 1 -Z 4 At least two of them are GeRR' or SiRR';

[0020] Each R A 、R D, R and R' are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, 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;

[0021] Ligand L A Complexation with metal M is shown by the dotted line to form a 5-membered chelate ring;

[0022] M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag and Au;

[0023] M can coordinate with other ligands;

[0024] L A capable of linking to other ligands to comprise tridentate, tetradentate, pentadentate, or hexadentate ligands; and

[0025] Any two adjacent R A 、R D , R and R' can all be joined or fused to form a ring.

[0026] In another aspect, the present disclosure provides formulations of compounds comprising ligand LA of Formula I as described herein.

[0027] In another aspect, the present disclosure provides an OLED having an organic layer comprising a compound comprising a ligand LA of Formula I as described herein.

[0028] In another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a ligand L comprising Formula I as described herein. A of compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 An organic light-emitting device is shown.

[0030] Figure 2 An inverted organic light-emitting device without a separate electron transport layer is demonstrated.

[0031] Figure 3 Shown are normalized PL spectra of the compounds of the present invention and comparative compounds in PMMA. DETAILED DESCRIPTION

[0032] A. Terminology

[0033] Unless otherwise specified, the following terms used herein are defined as follows:

[0034] 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 "small molecules" may actually be quite large. In some cases, small molecules may include repeating units. For example, the use of long-chain alkyl groups as substituents does not remove a molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, for example as side groups on the polymer backbone or as part of the backbone. Small molecules can also serve as the core part of a dendrimer, which consists of a series of chemical shells built on the core part. The core part of a dendrimer can be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be "small molecules", and all dendrimers currently used in the field of OLEDs are considered to be small molecules.

[0035] As used herein, "top" means farthest from the substrate, while "bottom" means closest to the substrate. When 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, other layers may be present between the first and second layers. For example, the cathode may be described as being "disposed above" the anode even if various organic layers are present between the cathode and the anode.

[0036] 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.

[0037] When a ligand is believed to directly contribute to the photosensitive properties of an emissive material, the ligand may be referred to as "photosensitive." When a ligand is believed not to contribute to the photosensitive properties of an emissive material, the ligand may be referred to as "ancillary," but the ancillary ligand may modify the properties of the photosensitive ligand.

[0038] 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 ionization potential (IP) is measured as 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.

[0039] As used herein, and as will generally be understood by those skilled in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Because work functions are 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 further away from the vacuum level in a downward direction. Therefore, the definitions of HOMO and LUMO energy levels follow different rules than those for work functions.

[0040] The terms "halo," "halogen," and "halo" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0041] The term "acyl" refers to a substituted carbonyl (C(O)-R s ).

[0042] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s OR-C(O)-OR s ) group.

[0043] The term "ether" refers to -OR s group.

[0044] The terms "thio" or "thioether" are used interchangeably and refer to -SR s group.

[0045] The term "sulfinyl" refers to -S(O)-R s group.

[0046] The term "sulfonyl" refers to -SO2-R s group.

[0047] The term "phosphino" refers to -P(R s )3 groups, wherein each R s Can be the same or different.

[0048] The term "silyl" refers to -Si(R s )3 groups, wherein each R s Can be the same or different.

[0049] 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.

[0050] In each of the above, R s and R is 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.

[0051] The term "alkyl" refers to and includes straight-chain and branched 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, and the like. In addition, the alkyl group may be optionally substituted.

[0052] The term "cycloalkyl" refers to and includes monocyclic, polycyclic and spiroalkyl groups. Preferred cycloalkyl groups are those 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 and the like. In addition, the cycloalkyl group may be optionally substituted.

[0053] 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.

[0054] 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.

[0055] The term "alkynyl" refers to and includes straight and branched chain alkynyl groups. An alkynyl group is essentially an alkyl group that includes at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. In addition, an alkynyl group may be optionally substituted.

[0056] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group. Additionally, an aralkyl group may be optionally substituted.

[0057] 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 groups. 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, and cyclic ethers / thioethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. In addition, the heterocyclic group can be optionally substituted.

[0058] The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. Polycyclic rings can have two or more rings in which two carbon atoms are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, for example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocycle 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. Especially preferred are aryl groups with six carbon atoms, ten carbon atoms or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthren, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted.

[0059] The term "heteroaryl" refers to and encompasses 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 having 5 or 6 ring atoms, and the rings may have from 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 group, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle, and / or heteroaryl groups. Heteropolycyclic aromatic ring systems may have from one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from three to thirty carbon atoms, preferably from three to twenty carbon atoms, and more preferably from three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazole In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof.

[0060] 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 aza analogs are of particular interest.

[0061] 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.

[0062] In many cases, the general substituent is 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, boryl, and combinations thereof.

[0063] In some cases, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, boryl, and combinations thereof.

[0064] In some cases, more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, thio, and combinations thereof.

[0065] In other cases, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0066] The terms "substituted" and "substituted" refer to substituents other than H being bonded to the relevant position, 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 represents disubstituted, the two R 1 must not be H. Similarly, when R 1 When it represents zero or no substitution, R 1 For example, it can be hydrogen with available valences for the ring atoms, such as the carbon atoms in 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 among the ring atoms.

[0067] 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 conceive from the applicable list. For example, alkyl and deuterium can combine to form partially or fully deuterated alkyl; halogen and alkyl can combine to form a haloalkyl substituent; and halogen, alkyl, and aryl can combine to form a haloaralkyl substituent. In one example, the term substituted includes a combination of two to four of the listed groups. In another example, the term substituted includes a combination of two to three groups. In yet another example, the term substituted 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 that include up to forty atoms that are not hydrogen or deuterium, or combinations that include 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.

[0068] 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 limitation, azatriphenylene encompasses dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the term as set forth herein.

[0069] 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 deuterated organometallic complexes. With further reference 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) describe the deuteration of methylene hydrogen in benzylamine and the effective way to replace aromatic ring hydrogen with deuterium.

[0070] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name can be written as if it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attaching fragments are considered equivalent.

[0071] In some cases, a pair of adjacent substituents may be optionally joined or fused to form a ring. Preferred rings are five-, six-, or seven-membered carbocyclic or heterocyclic rings, including those in which 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 may be immediately adjacent to each other on the same ring, or on two adjacent rings with the 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.

[0072] B. Compounds of the Disclosure

[0073] In one aspect, the present disclosure provides a compound comprising a ligand LA of Formula I:

[0074]

[0075] in

[0076] A 1 and A 2 each independently a monocyclic or polycyclic fused ring system comprising one or more fused or non-fused 5- or 6-membered carbocyclic or heterocyclic rings;

[0077] X 1 -X 4 are independently C or N, with the proviso that X 1 -X 4 At least one of them is C and X 1 -X 4 At least one of them is N;

[0078] K 1 and K 2 are each independently selected from the group consisting of: a direct bond, O, and S;

[0079] L 1 selected from the group consisting of a single bond, O, S, C═R′, CR′R″, SiR′R″, GeRR′, BR′, BR′R″, and NR′;

[0080] R A and R D Each represents zero substitution, monosubstitution, or up to the maximum allowable substitution on its associated ring;

[0081] R A and R D At least one of them has a structure of formula II, which is the same as the corresponding A 1 and A 2 condensed;

[0082]

[0083] Z 1 -Z 4 Each independently selected from the group consisting of: CRR', SiRR' and GeRR', with the proviso that Z 1 -Z 4 At least one of them is GeRR' or SiRR';

[0084] n = 0 or 1;

[0085] When n is 1 and A 1 or A 2 When Z is a pyridine ring fused to Formula II, 1 -Z 4 At least two of them are GeRR' or SiRR';

[0086] Each R A 、R D , R and R' are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, 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;

[0087] Ligand L A Complexation with metal M is shown by the dotted line to form a 5-membered chelate ring;

[0088] M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag and Au;

[0089] M can coordinate with other ligands;

[0090] L A capable of linking to other ligands to form tridentate, tetradentate, pentadentate, or hexadentate ligands; and

[0091] Any two adjacent R A 、R D , R and R' can all be joined or fused to form a ring.

[0092] In some embodiments, the compounds of the present disclosure comprise a ligand L of Formula IV A :

[0093]

[0094] Ring A 1 Ring A 2 、X 1 -X 4 、R A and R Dis as defined above.

[0095] In some embodiments, each R A 、R D , R and R' are independently hydrogen or a common or preferred general substituent disclosed above.

[0096] In some embodiments, n is 0. In some embodiments, n is 1.

[0097] In some embodiments, K 1 is a direct key. In some embodiments, K 2 is a direct key. In some embodiments, K 1 Is 0. In some embodiments, K 2 Is 0. In some embodiments, K 1 is S. In some embodiments, K 2 is S. In some embodiments, L 1 is a direct key. In some embodiments, L 1 is O. In some embodiments, L 1 is S. In some embodiments, L 1 is CR'R". In some embodiments, L 1 is SiR'R". In some embodiments, L 1 is BR'. In some embodiments, L 1 is NR'. In some embodiments, K 1 and K 2 One of them is a direct key, K 1 and K 2 The other of is O or S. In some embodiments, L 1 , K 1 , K 2 In some embodiments, L 1 It is a direct key, K 1 and K 2 One of them is a direct key, K 1 and K 2 The other of is O or S. In some embodiments, L 1 It is a direct key, K 1 and K 2 One of them is a direct key, K 1 and K 2 The other of is O or S. In some embodiments, L 1 Selected from the group consisting of: O, S, C═R′, CR′R″, SiR′R″, GeRR′, BR′, BR′R″, and NR′; K 1 and K 2 They are all direct keys.

[0098] In some embodiments, A 1 and A 2 One of them is benzene, and A 1 and A 2 The other of the group consisting of: pyrimidine, pyridine, pyridazine, triazine, pyrazine, benzene, imidazole, pyrazole, oxazole, thiazole and N-heterocyclic carbene.

[0099] In some embodiments, Z 1 -Z 4 One of them is SiRR', and Z 1 -Z 4 The rest of them are CRR'.

[0100] In some embodiments, Z 1 -Z 4 Two of them are SiRR', and Z 1 -Z 4 The rest of them are CRR'.

[0101] In some embodiments, R and R' are each independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0102] In some embodiments, when R and R' are attached to the same Si atom, R and R' are joined together to form a ring.

[0103] In some embodiments, X 1 is N and X 2 、X 3 and X 4 Each is C.

[0104] In some embodiments, one or more R D The substituent is an alkyl group.

[0105] In some embodiments, M is Ir.

[0106] In some embodiments, the compound further comprises a substituted or unsubstituted acetylacetonate ligand.

[0107] In some embodiments, the ligand L A is selected from the group consisting of the structures in List A below:

[0108]

[0109] in:

[0110] T is selected from the group consisting of B, Al, Ga and In;

[0111] Y 1 To Y 13 each of which is independently selected from the group consisting of: carbon and nitrogen;

[0112] 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 ;

[0113] R e and R f capable of being fused or joined to form a ring;

[0114] Each R a 、R b 、R c and R d independently represents zero substitution, monosubstitution, or up to the maximum allowed number of substitutions on its associated ring;

[0115] R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e and R f each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; general substituents as defined herein; and

[0116] Any two adjacent R a 、R b 、R c 、R d 、R e and R f Can be fused or joined to form a ring or to form a multidentate ligand.

[0117] In some embodiments, the ligand L A is selected from the group consisting of the structures in List B below:

[0118]

[0119]

[0120]

[0121] In some embodiments, Formula II is selected from the group consisting of:

[0122]

[0123] wherein R and R' are capable of forming a ring; and R and R' are selected from the group consisting of:

[0124]

[0125]

[0126] In some embodiments, the ligand L A is selected from the group consisting of the structures in List C below:

[0127] based on L Ai-1 ,based on L Ai-2 ,based on L Ai-3 、

[0128] based on L Ai-4 ,based on L Ai-5 ,based on L Ai-6 、

[0129] based on L Ai-7 ,based on L Ai-8 ,based on L Ai-9 、

[0130] based on L Ai-10 ,based on L Ai-11 、

[0131] based on L Ai-12 ,based on L Ai-14 、

[0132] based on L Ai-15 ,based on L Ai-16 、

[0133] based on L Ai-17 ,based on L Ai-18 、

[0134] based on L Ai-19 ,based on L Ai-20 、

[0135] based on L Ai-21 ,based on L Ai-22 、

[0136] based on L Ai-23 ,based on L Ai-24 、

[0137] based on L Ai-25 ,based on L Ai-26 、

[0138] based on L Ai-27 ,based on L Ai-28 、

[0139] based on L Ai-29 ,based on L Ai-30 、

[0140] based on L Ai-31 ,based on L Ai-32 、

[0141] based on L Ai-33 ,based on L Ai-34 、

[0142] based on L Ai-35 ,based on L Ai-36 、

[0143] based on L Ai-37 ,based on L Ai-38 、

[0144] based on L Ai-39 ,based on L Ai-40 、

[0145] based on L Ai-41 ,based on L Ai-42 、

[0146] based on L Ai-43 ,based on L Ai-44 、

[0147] based on L Ai-45 ,based on L Ai-46 、

[0148] based on L Ai-47 ,based on L Ai-48 、

[0149] based on L Ai-49 ,based on L Ai-50 、

[0150] based on L Ai-51 ,based on L Ai-52 、

[0151] based on L Ai-53 ,based on L Ai-54 、

[0152] based on L Ai-55 ,based on L Ai-56 、

[0153] based on L Ai-57 ,based on L Ai-58 、

[0154] based on L Ai-59 ,based on L Ai-60 、

[0155] based on L Ai-61 ,based on L Ai-62 、

[0156] based on L Ai-63 ,based on L Ai-64 、

[0157] based on L Ai-65 ,based on L Ai-66 、

[0158] based on L Ai-67 and based on L Ai-68 , where i is an integer from 1 to 698, and for each i, R E and G are as defined in Table 1 below:

[0159]

[0160]

[0161]

[0162]

[0163]

[0164] where R 1 to R 43 Has the following structure: and

[0165] Among them G 1 to G 22 Has the following structure:

[0166]

[0167] In some embodiments, the compound has the formula M(L A ) x (L B ) y (L C ) z , where L B and L CEach is a bidentate ligand; and wherein x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M.

[0168] In some embodiments, the compound has a formula selected from the group consisting of: Ir(L A )3、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 ); and wherein L A , L B and L C Different from each other.

[0169] In some embodiments, the compound has the formula Pt(L A )(L B ); and L A and L B Can be the same or different.

[0170] In some embodiments, L A and L B connected to form a tetradentate ligand.

[0171] In some embodiments, L A and L B ligated at two positions to form a macrocyclic tetradentate ligand.

[0172] In some embodiments, L B is selected from the group consisting of the structures in List A defined above.

[0173] In some embodiments, L B and L C Each is independently selected from the group consisting of the structures in List D below:

[0174]

[0175]

[0176]

[0177]

[0178] where R a '、R b '、R c '、R d'、R e '、R f '、R g ' and R n 'Each independently represents zero substitution, monosubstitution, or up to the maximum permissible substitution on its associated ring;

[0179] R a '、R b '、R c '、R d '、R e '、R f '、R g ' and R n 'are each independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof;

[0180] Two adjacent R a '、R b '、R c '、R d '、R e '、R f '、R g ' and R n ' can be fused or joined to form a ring or to form a multidentate ligand; and

[0181] R a 、R b and R c are all defined the same as above, and each of them can form a ring with another when chemically feasible.

[0182] 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 B Choose from L Bk A group consisting of, wherein k is an integer from 1 to 270, wherein L B1 To L B270 With the following structure defined in Listing E:

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192] 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 B is 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 B132 , L B134 , L B136 , L B138 , L B140 , L B142 , L B144 , L B156 , L B158 , 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 , L B250 , L B252 , L B254 , L B256 , L B258 , L B260 , L B262 , L B263 , L B264 , L B265 , L B266 , L B267 , L B268 , L B269 and L B270 .

[0193] 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 B is selected from the group consisting of: L B1 , L B2 , L B18 , L B28 , L B38 , L B108 , L B118 , L B122 , 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 , L B237 , L B264 , L B265 , L B266 , L B267 , L B268 , L B269 and L B270 .

[0194] 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 C is a substituted or unsubstituted acetyl acetonate ligand. In some embodiments, L C Is to choose L Cj-I and L Cj-II A group consisting of, where j is an integer from 1 to 1416, where L Cj-I Based on The structure of L C1-I To L C1416-I The compound composition, and L Cj-II Based on The structure of L C1-II To L C1416-II The compound composition, among which L Cj-I and L Cj-II Each L in Cj , R 201 and R 202 Each is independently defined in Table 2 below:

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203] where R D1 to R D246 With the following structure in Listing F:

[0204]

[0205]

[0206]

[0207]

[0208] In the case of a product having the formula M(L A ) x (L B ) y (LC ) z In some embodiments of the compound, the ligand L C can be selected from only the corresponding R 201 and R 202 L is defined as one of the following structures Cj-I or L Cj-II Ligand group: RD 1 , RD 3 , RD 4 , RD 5 , RD 9 , RD 10 , RD 17 , RD 18 , RD 20 , RD 22 , RD 37 , RD 40 , RD 41 , RD 42 , RD 43 , RD 48 , RD 49 , RD 50 , RD 54 , RD 55 , RD 58 , RD 59 , RD 78 , RD 79 , RD 81 , RD 87 , RD 88 , RD 89 , RD 93 , RD 116 , RD 117 , RD 118 , RD 119 , RD 120 , RD 133 , RD 134 , RD 135 , RD 136 , RD 143 , RD 144 , RD 145 , RD 146 , RD 147 , RD 149 , RD 151 , RD 154 , RD 155 , RD 161 , RD 175 , RD 190 , RD 193 , RD 200 , RD 201 , RD206 , RD 210 , RD 214 , RD 215 , RD 216 , RD 218 , RD 219 , RD 220 , RD 227 , RD 237 , RD 241 , RD 242 , RD 245 and RD 246 .

[0209] 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 ligand L C can be selected from only the corresponding R 201 and R 202 L is defined as one selected from the following structures Cj-I or L Cj-II Ligand group: RD 1 , RD 3 , RD 4 , RD 5 , RD 9 , RD 10 , RD 17 , RD 22 , RD 43 , RD 50 , RD 78 , RD 116 , RD 118 , RD 133 , RD 134 , RD 135 , RD 136 , RD 143 , RD 144 , RD 145 , RD 146 , RD 149 , RD 151 , RD 154 , RD 155 , RD 190 , RD 193 , RD 200 , RD 201 , RD 206 , RD 210 , RD 214 , RD 215 , RD 216, RD 218 , RD 219 , RD 220 , RD 227 , RD 237 , RD 241 , RD 242 , RD 245 and RD 246 .

[0210] 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 ligand L C You can choose from the following groups:

[0211]

[0212]

[0213] In some embodiments, the compound is selected from the group consisting of: based on the general formula Ir(L Ai-m )3 of Ir(L A1-1 )3 to Ir(L A698-68 )3; Based on the general formula Ir(L Ai-m )(L Bk )2 of Ir(L A1-1 )(L B1 )2 to Ir(L A698-68 )(L B270 )2; Based on the general formula Ir(L Ai-m )2(L Cj-I ) of Ir(L A1-1 )2(L C1-I ) to Ir(L A698-68 )2(L C1416-I ); and based on the general formula Ir(L Ai-m )2(L Cj-II ) of Ir(L A1-1 )2(L C1-II ) to Ir(L A698-68 )2(L C1416-II ); wherein i is an integer from 1 to 698, m is an integer from 1 to 68, k is an integer from 1 to 270, j is an integer from 1 to 1416, wherein each L Ai-m , L Bk , L Cj-I and L Cj-II is as defined above.

[0214] In some embodiments, the compound is selected from the group consisting of the structures in List G below:

[0215]

[0216]

[0217]

[0218]

[0219] In some embodiments, the compound may have a formula based on Ir(L Ai-m )(L B )2 formula Ir(L A1-1 )(L B )2 to Ir(L A698-68 )(L B )2, where L Ai-m is selected from L as described above A1-1 To L A698-68 The structure of the group composed of B is selected from the group consisting of the structures in List A above.

[0220] In some embodiments, the compound may have a formula based on Ir(L A )(L Bk )2 formula Ir(L A )(L B1 )2 to Ir(L A )(L B2770 )2, where L A having the formula I described above, and L Bk represents L as described above B1 To L B270 structure.

[0221] In some embodiments, the compound may have a formula based on Ir(L Ai-m )2(L B ) of the formula Ir(L A1-1 )2(L B ) to Ir(L A698-68 )2(L B ), where L Ai-m Represented by L as described above A1-1 To L A698-68 The group is composed of B is selected from the group consisting of the structures listed in List A above.

[0222] In some embodiments, the compound may have a formula based on Ir(L A )2(LBk ) of the formula Ir(L A )2(L B1 ) to Ir(L A )2(L B270 ), where L A having the formula I described above, and L Bk represents L as described above B1 To L B270 One of the structures.

[0223] In some embodiments, the compound may have a formula based on Ir(L Ai-m )2(L C ) of the formula Ir(L A1-1 )2(L C ) to Ir(L A698-68 )2(L C ), where L Ai-m Represents L as described above A1-1 To L A698-68 The group is composed of C is selected from the group consisting of the structures listed in List B above.

[0224] In some embodiments, the compound may have a formula based on Ir(L A )2(L Cj-I ) of the formula Ir(L A )2(L C1-I ) to Ir(L A )2(L C1416-I ), where L A having the formula I described above, and L Cj-I represents L as described above C1-I To L C1416-I One of the structures.

[0225] In some embodiments, the compound may have a formula based on Ir(L A )2(L Cj-II ) of the formula Ir(L A )2(L C1-II ) to Ir(L A )2(L C1416-II ), where L A having the formula I described above, and L Cj-II represents L as described above C1-II To L C1416-II One of the structures.

[0226] In some embodiments, the compound has Formula III:

[0227]

[0228] in:

[0229] M 1 is Pd or Pt;

[0230] Moieties E and F are each independently a monocyclic or polycyclic structure comprising a 5-membered and / or 6-membered carbocyclic or heterocyclic ring;

[0231] Z 1 and Z 2 are each independently C or N;

[0232] K 1 , K 2 , K 3 and K 4 are each independently selected from the group consisting of: a direct bond, O, and S, wherein the K 1 , K 2 , K 3 and K 4 At least two of them are direct bonds;

[0233] L 1 , L 2 , L 3 and L 4 are each independently selected from the group consisting of a single bond, no bond, O, S, CR'R", SiR'R", BR' and NR', wherein L is present 1 , L 2 , L 3 and L 4 At least three of R E and R F Each independently represents zero substitution, monosubstitution, or up to the maximum allowed number of substitutions on its associated ring;

[0234] R', R", R E and R F each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof;

[0235] When chemically feasible, two adjacent R A 、R D 、R E and R F capable of joining or fusion together to form a ring; and

[0236] X 1 -X 4 、R A 、R Dand Ring A 1 and A 2 In some embodiments, Ring E and Ring F are both 6-membered aromatic rings.

[0237] In some embodiments, Ring F is a 5-membered or 6-membered heteroaryl ring. 2 is O or CR'R". In some embodiments, Z 2 is N and Z 1 is C. In some embodiments, Z 2 Is C and Z 1 is N. In some embodiments, L 3 is a direct key. In some embodiments, L 3 is NR'. In some embodiments, K 1 , K 2 , K 3 and K 4 In some embodiments, K 1 , K 2 , K 3 and K 4 One of them is O.

[0238] In some embodiments, the compound is selected from the group consisting of:

[0239]

[0240]

[0241] in:

[0242] R x and R y each selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;

[0243] R G is independently at each occurrence hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof; and

[0244] X 1 -X 4 、R A 、R D and Ring A 1 and A 2 All are defined the same as above.

[0245] C. OLEDs and Devices of the Present Disclosure

[0246] 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.

[0247] In some embodiments, the first organic layer may include a ligand L comprising Formula I A of compounds.

[0248] In some embodiments, the organic layer can be an emissive layer and the compound as described herein can be an emissive dopant or a non-emissive dopant.

[0249] 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.

[0250] In some embodiments, the organic layer further comprises a host, wherein the host comprises at least one chemical moiety selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene, azatriphenylene, azacarbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene).

[0251] In some embodiments, the subject can be selected from the group consisting of:

[0252]

[0253]

[0254]

[0255] and combinations thereof.

[0256] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.

[0257] In some embodiments, the compound as described herein can be a sensitizer; wherein the device can further comprise a receptor; and wherein the receptor can be selected from the group consisting of: a fluorescent emitter, a delayed fluorescent emitter, and combinations thereof.

[0258] In another aspect, the OLED of the present disclosure may further comprise an emissive region comprising a compound as disclosed in the above compounds section of the present disclosure.

[0259] In some embodiments, the emission region may comprise a ligand L comprising Formula I A of compounds.

[0260] In some embodiments, at least one of an anode, cathode, or new layer disposed above the organic emissive layer serves as an enhancement layer. The enhancement layer comprises a plasmon material exhibiting surface plasmon resonance, the plasmon material non-radiatively couples to the emitter material, and transfers excited-state energy from the emitter material to a non-radiative mode of a surface plasmon polariton. The enhancement layer is disposed at a distance from the organic emissive layer that does not exceed a threshold distance, wherein due to the presence of the enhancement layer, the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant, and the threshold distance is the position where the total non-radiative decay rate constant equals the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the enhancement layer on an opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on the side of the emissive layer opposite the enhancement layer, but is still capable of outcoupling energy from the surface plasmon modes of the enhancement layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered into free space as photons. In other embodiments, energy is scattered from the surface plasmon modes of the device into other modes, such as, but not limited to, organic waveguide modes, substrate modes, or another waveguide mode. If energy is scattered into non-free-space modes of the OLED, other outcoupling schemes can be incorporated to extract the energy into free space. In some embodiments, one or more intervening layers can be positioned between the enhancement layer and the outcoupling layer. Examples of intervening layers can be dielectric materials, including organic, inorganic, perovskite, oxides, and can include stacks and / or mixtures of these materials.

[0261] The enhancement layer modifies the effective properties of the medium in which the emitter material resides, resulting in any or all of the following: reduced emissivity, altered emission line shape, variation in emission intensity with angle, altered emitter material stability, altered OLED efficiency, and reduced roll-off efficiency of the OLED device. Placing the enhancement layer on the cathode side, the anode side, or both produces an OLED device that exploits any of the aforementioned effects. In addition to the specific functional layers described herein and illustrated in the various OLED examples shown in the figures, OLEDs according to the present disclosure may also include any other functional layers commonly found in OLEDs.

[0262] The enhancement layer may comprise a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material comprises at least one metal. In such embodiments, the metal may comprise at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. In general, a metamaterial is a medium composed of different materials, where the effect of the medium as a whole is different from the sum of its material parts. Specifically, we define an optically active metamaterial as a material that has both negative permittivity and negative permeability. On the other hand, a hyperbolic metamaterial is an anisotropic medium in which the permittivity or permeability has different signs for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are distinct from many other photonic structures, such as distributed Bragg reflectors (DBRs), because the dielectric should appear uniform in the direction of propagation on the length scale of the light wavelength. Using terminology understood by those skilled in the art, the dielectric constant of a metamaterial in the direction of propagation can be described using the effective dielectric approximation. Plasmonic and metamaterials offer methods for controlling light propagation, which can enhance OLED performance in a variety of ways.

[0263] In some embodiments, the reinforcement layer is configured as a planar layer. In other embodiments, the reinforcement layer has wavelength-sized features arranged periodically, quasi-periodically, or randomly, or has sub-wavelength-sized features arranged periodically, quasi-periodically, or randomly. In some embodiments, the wavelength-sized features and sub-wavelength-sized features have sharp edges.

[0264] In some embodiments, the outcoupling layer has wavelength-sized features that are periodically, quasi-periodically, or randomly arranged, or has sub-wavelength-sized features that are periodically, quasi-periodically, or randomly arranged. In some embodiments, the outcoupling layer can be composed of a plurality of nanoparticles, and in other embodiments, the outcoupling layer can be composed of a plurality of nanoparticles disposed above a material. In these embodiments, outcoupling can be adjusted by at least one of: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material or an additional layer disposed above the plurality of nanoparticles, changing the thickness of the enhancement layer, and / or changing the material of the enhancement layer. The plurality of nanoparticles of the device can be formed from at least one of a metal, a dielectric material, a semiconductor material, a metal alloy, a mixture of dielectric materials, a stack or layer of one or more materials, and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. Multiple nanoparticles can have additional layers disposed above them. In some embodiments, the outcoupling layer can be used to adjust the polarization of the emission. Varying the size and periodicity of the outcoupling layer can select the polarization type that preferentially couples to air. In some embodiments, the outcoupling layer also serves as an electrode for the device.

[0265] In another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compound section of the present disclosure.

[0266] In some embodiments, a consumer product comprises an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound comprising a ligand LA of Formula I as described herein.

[0267] 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 phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a video camera, 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.

[0268] 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 photoemission 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.

[0269] Several OLED materials and configurations are described in US Patent Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

[0270] 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 timeframe of less than 10 nanoseconds.

[0271] 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.

[0272] Figure 1 An organic light-emitting device 100 is shown. The figure is not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a blocking layer 170. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. 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 Pat. No. 7,279,704, columns 6-10, which is incorporated by reference.

[0273] 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 entireties, 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 entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0274] 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 fabricated by depositing the layers in order. Because the most common OLED configuration has the cathode positioned above the anode, and device 200 has cathode 215 positioned below anode 230, device 200 can be referred to as an "inverted" OLED. Materials similar to those described for 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 .

[0275] Figure 1 and 2The simple layered structures illustrated in the are provided by way of non-limiting examples, and it will be appreciated 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 layers may be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe the various layers as comprising a single material, it will be appreciated that combinations of materials may be used, such as mixtures of hosts and dopants, or more generally, mixtures. In addition, the layers may have various sub-layers. 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 the cathode and the anode. This organic layer may comprise a single layer, or may further comprise, for example, a layer comprising a plurality of layers. Figure 1 and 2 Multiple layers of said different organic materials.

[0276] Structures and materials not specifically described may also be used, such as OLEDs comprising 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.

[0277] 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. Patents Nos. 6,013,982 and 6,087,196, incorporated by reference in their entirety), organic vapor phase deposition (OVPD) (as described in U.S. Patent No. 6,337,102 to Forrest et al., incorporated by reference in its entirety), and deposition by organic vapor jet printing (OVJP) (as described in U.S. Patent No. 7,431,968, incorporated by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding (as described in U.S. Patents 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 the 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 with 20 or more carbons may be used, and 3 to 20 carbons are a preferred range. Materials with asymmetric structures may have better solution processability than materials with symmetrical structures because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to withstand solution processing.

[0278] 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 damage by harmful substances in the environment including moisture, steam and / or gas. The barrier layer can be deposited on the substrate, the electrode, under the substrate, the electrode, or next to the substrate, the electrode, or on any other part of the device (including the edge). The barrier layer may comprise a single layer or multiple layers. The barrier layer can be formed by various known chemical vapor deposition techniques and may include compositions having a single phase and compositions having multiple phases. Any suitable material or combination of materials can be used for the barrier layer. The barrier layer may be combined with an inorganic compound or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material, as described in U.S. Patent No. 7,968,146, PCT Patent Application No. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. To be considered a "mixture," the aforementioned polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and / or deposited simultaneously. The weight ratio of polymeric to non-polymeric materials can range from 95:5 to 5:95. The polymeric and non-polymeric materials can be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

[0279] The devices manufactured according to the embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units), which can be incorporated into a wide 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 utilized by end-user product manufacturers. The electronic component modules can optionally include driving electronic devices and / or power supplies. The devices manufactured according to the embodiments of the present disclosure can be incorporated into a wide variety of consumer products, which have one or more electronic component modules (or units) incorporated therein. A consumer product comprising an OLED is disclosed, wherein 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 some type of visual display. Some examples of such 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, telephones, 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 matrix and active matrix. 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).

[0280] More details regarding OLEDs and the definitions described above can be found in US Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0281] The materials and structures described herein can be used in 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.

[0282] In some embodiments, the OLED has one or more characteristics 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.

[0283] 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.

[0284] In some embodiments, the compound can be an emitting dopant. In some embodiments, the compound can produce emission 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 a kind of enantiomer. In some embodiments, the compound can be homogeneous (each ligand is identical). In some embodiments, the compound can be mixed (at least one ligand is different from 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 also holds true in the embodiment where the ligand coordinated to the metal can be connected to form a tridentate, quadridentate, pentadentate, or hexadentate ligand with other ligands coordinated to the metal. 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).

[0285] 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 exciplex 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 range from 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.

[0286] According to another aspect, a formulation comprising a compound described herein is also disclosed.

[0287] The OLEDs disclosed herein can be incorporated into one or more of consumer products, electronic component modules, and lighting panels.The organic layer can be an emissive layer, and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.

[0288] 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.

[0289] 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 supermolecules). As used herein, a "monovalent variant of a compound" refers to a portion that is identical to the compound but has one hydrogen 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 has more than one hydrogen removed and replaced with one or more bonds to the rest of the chemical structure. In the case of supramolecules, the compounds of the present invention can also be incorporated into supramolecular complexes without covalent bonds.

[0290] In some embodiments, at least one of an anode, cathode, or new layer disposed on the organic emissive layer functions as an enhancement layer. The enhancement layer comprises a plasmonic material exhibiting surface plasmon resonance that non-radiatively couples to the emitter material and transfers excited-state energy from the emitter material to non-radiative modes of surface plasmon polaritons. The enhancement layer is provided at no more than a threshold distance from the organic emissive layer, wherein due to the presence of the enhancement layer, the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant, and the threshold distance is the distance at which the total non-radiative decay rate constant equals the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the organic emissive layer from the enhancement layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the emissive layer from the enhancement layer, but still couples energy from the surface plasmon modes of the enhancement layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered into free space in the form of photons. In other embodiments, the energy is scattered from the surface plasmon mode to other modes of the device, such as, but not limited to, an organic waveguide mode, a substrate mode, or another waveguide mode. If the energy is scattered to a non-free-space mode of the OLED, other outcoupling schemes may be incorporated to extract the energy to free space. In some embodiments, one or more intervening layers may be disposed between the enhancement layer and the outcoupling layer. Examples of intervening layers include dielectric materials, including organics, inorganics, perovskites, oxides, and may include stacks and / or mixtures of these materials.

[0291] The enhancement layer modifies the effective properties of the medium in which the emitter material resides, resulting in any or all of the following: reduced emissivity, modification of the emission line shape, changes in emission intensity versus angle, changes in the stability of the emitter material, changes in the efficiency of the OLED, and reduced efficiency roll-off of the OLED device. Placing the enhancement layer on the cathode side, the anode side, or both sides results in an OLED device that utilizes any of the aforementioned effects. In addition to the specific functional layers described herein and illustrated in the various OLED examples shown in the figures, OLEDs according to the present disclosure may also include any of the other functional layers typically found in OLEDs.

[0292] The enhancement layer can be composed of a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. As used herein, a plasmonic material is a material whose real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material comprises at least one metal. In such embodiments, the metal may include at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca alloys, or mixtures of these materials, as well as stacks of these materials. Generally speaking, a metamaterial is a medium composed of different materials, where the medium as a whole behaves differently than the sum of its component materials. Specifically, we define an optically active metamaterial as a material having both a negative dielectric constant and a negative magnetic permeability. On the other hand, a hyperbolic metamaterial is an anisotropic medium whose dielectric constant or magnetic permeability has different signs for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are distinct from many other photonic structures, such as distributed Bragg reflectors (DBRs), because the dielectric must be uniform along the direction of propagation for the length scale of the light's wavelength. Using terminology understood by those skilled in the art, the dielectric constant of a metamaterial in the direction of propagation can be described by the effective dielectric approximation. Plasmonic and metamaterial materials offer a method for controlling light propagation that can enhance OLED performance in a variety of ways.

[0293] In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has periodic, quasi-periodic, or randomly arranged wavelength-sized features, or periodic, quasi-periodic, or randomly arranged sub-wavelength-sized features. In some embodiments, the wavelength-sized features and sub-wavelength-sized features have sharp edges.

[0294] In some embodiments, the outcoupling layer has wavelength-sized features that are periodically, quasi-periodically, or randomly arranged, or sub-wavelength-sized features that are periodically, quasi-periodically, or randomly arranged. In some embodiments, the outcoupling layer may be composed of a plurality of nanoparticles, and in other embodiments, the outcoupling layer may be composed of a plurality of nanoparticles disposed on a material. In these embodiments, the outcoupling may be tuned by at least one of: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, changing the thickness of the enhancement layer, and / or changing the material of the enhancement layer. The plurality of nanoparticles of the device may be formed from at least one of: a metal, a dielectric material, a semiconductor material, a metal alloy, a mixture of dielectric materials, a stack or layering of one or more materials, and / or a core of one type of material coated with a shell of a different type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. Multiple nanoparticles can have additional layers disposed thereon. In some embodiments, the polarization of the emission can be tuned using the outcoupling layer. Varying the dimensionality and periodicity of the outcoupling layer can select a polarization that preferentially couples to air. In some embodiments, the outcoupling layer also serves as an electrode for the device.

[0295] D. Combinations of Compounds of the Disclosure with Other Materials

[0296] The materials described herein as suitable for use in a particular layer of 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 readily consult the literature to identify other materials that can be used in combination.

[0297] a) Conductive dopant:

[0298] The charge transport layer can be doped with a conductivity dopant to substantially alter its charge carrier density, which in turn will alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor 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.

[0299] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with the references disclosing those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.

[0300]

[0301]

[0302] b)HIL / HTL:

[0303] 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; indolocarbazole derivatives; polymers containing fluorocarbons; polymers having a conductive dopant; conductive polymers such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x ; p-type semiconducting organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes; and cross-linkable compounds.

[0304] Examples of aromatic amine derivatives for use in HILs or HTLs include, but are not limited to, the following general structure:

[0305]

[0306] 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, which 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.

[0307] In one aspect, Ar 1 to Ar 9 Independently selected from the group consisting of:

[0308]

[0309] Where 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.

[0310] Examples of metal complexes used in the HIL or HTL include, but are not limited to, the following general formula:

[0311]

[0312] Wherein Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 Independently selected from C, N, O, P and S; L 101is 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.

[0313] 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 + The minimum oxidation potential in solution due to the / Fc coupling is less than about 0.6 V.

[0314] 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 to those materials 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. ,

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322] c) EBL:

[0323] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime compared to a similar device lacking the 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.

[0324] d) Subject:

[0325] 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 can be used as long as the triplet energy of the host is greater than the triplet energy of the dopant. Any host material can be used with any dopant as long as the triplet criterion is met.

[0326] Examples of metal complexes used as hosts preferably have the following general formula:

[0327]

[0328] Wherein Met is a metal; (Y 103 -Y 104) is a bidentate ligand, Y 103 and Y 104 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.

[0329] In one aspect, the metal complex is:

[0330]

[0331] where (ON) is a bidentate ligand with a metal coordinated to O and N atoms.

[0332] In another aspect, Met is selected from Ir and Pt. In another aspect, (Y 103 -Y 104 ) is a carbene ligand.

[0333] 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, which 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.

[0334] In one aspect, the subject compound contains at least one of the following groups in the molecule:

[0335]

[0336]

[0337] 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.

[0338] 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,

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345] e) Other emitters:

[0346] 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 can 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.

[0347] 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, JP2013110263, 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。、

[0348]

[0349]

[0350]

[0351]

[0352]

[0353] f)HBL:

[0354] 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 compared to a similar device lacking the blocking layer. In addition, a blocking layer can be used to confine emission to desired areas 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.

[0355] In one aspect, the compounds used in HBL contain the same molecules or the same functional groups as used in the subjects described above.

[0356] In another aspect, the compound used in HBL contains at least one of the following groups in the molecule:

[0357]

[0358] Where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0359] g)ETL:

[0360] 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.

[0361] In one aspect, the compound used in the ETL contains at least one of the following groups in the molecule:

[0362]

[0363] where R 101is 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. 1 to Ar 3 has a similar definition to Ar mentioned above. k is an integer from 1 to 20. X 101 to X 108 is selected from C (including CH) or N.

[0364] In another aspect, the metal complex used in the ETL contains (but is not limited to) the following general formula:

[0365]

[0366] 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.

[0367] 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 US2009018179634. 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,

[0368]

[0369]

[0370]

[0371] h) Charge Generation Layer (CGL)

[0372] In tandem or stacked OLEDs, the CGL plays a fundamental role in performance. It 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. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductivity dopants used in the transport layer.

[0373] In any of the above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any of the specifically listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, etc., can 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.) can also be in their non-deuterated, partially deuterated, and fully deuterated forms.

[0374] 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, many materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the present invention. Therefore, the present invention as required can include variations of the 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.

[0375] experiment

[0376] Step 1: Synthesis of 1,2-bis(ethynyldimethylsilyl)ethane 2

[0377]

[0378] At 25 ° C, ethynyl magnesium chloride (499 mL, 250 mmol) was added dropwise via cannula to a stirred solution of 1,2-bis(chlorodimethylsilyl)ethane 1 (24 g, 111 mmol) in THF (400 mL) over a period of 90 minutes. After the addition was complete, the reaction was heated to 80 ° C and stirred at this temperature for 24 hours, at which time TLC analysis (10% EtOAc / isohexane) determined that the starting material was completely consumed. The reaction was carefully diluted with NHCl (saturated aqueous solution, 200 mL) and then EtO (200 mL) was added. The layers were partitioned, the aqueous phase was back-extracted with EtO (2×200 mL) and the combined organic extracts were washed with brine (saturated aqueous solution, 200 mL) and then passed through a phase separator cartridge. The crude material was concentrated directly onto silica and purified by column chromatography eluting with neat isohexane to 20% Et2O / isohexane to give the title compound 2 (19.0 g, 97.7 mmol) as a yellow oil.

[0379] Step 2: Synthesis of 1,1,4,4-tetramethyl-1,2,3,4-tetrahydrobenzo[b][1,4]disilane-6-carbaldehyde

[0380]

[0381] Iodine (0.50 g, 1.95 mmol) was added to a stirred suspension of zinc (1.28 g, 19.54 mmol) in CH3CN (175 mL). The brown color dissipated over 5 minutes, leaving a gray suspension that was stirred for another 45 minutes. The suspension was cooled to 5 ° C and 1,2-bis (ethynyldimethylsilyl) ethane 2 (19.0 g, 98 mmol) was added over 10 minutes, followed by 3,3-diethoxyprop-1-yne (19.6 mL, 137 mmol) over 5 minutes. Finally, a solution of CoBr2 (2.14 g, 9.77 mmol) in CH3CN (25 mL) was added over 10 minutes. The mixture turned brown over 20 minutes and was stirred at 25 ° C for 24 hours, after which TLC indicated that the starting material was completely consumed. The reactant was diluted with 2N HCl (aqueous solution, 2 equivalents, 100 mL) and stirred for 24 hours, at which point the reactant was diluted with water and EtOAc. The layers were separated and the aqueous phase was back extracted with EtOAc (2 times). The combined organic extracts were washed with brine (1 time), dried over MgSO4, concentrated directly onto silica and purified by column chromatography eluting with neat isohexane to 5% EtOAc to 10% EtOAc / isohexane to give the title compound (11.2 g, 45.1 mmol) as an orange oil.

[0382] Step 3: Synthesis of 1,1,4,4-tetramethyl-1,2,3,4-tetrahydrobenzo[b][1,4]disilane-6-carboxylic acid 5

[0383]

[0384] A mixture of 1,1,4,4-tetramethyl-1,2,3,4-tetrahydrobenzo[b][1,4]disilane-6-carbaldehyde 4 (11.2 g, 45.1 mmol) and potassium persulfate (27.7 g, 90 mmol) in DMF (180 mL) was stirred at 25 ° C for 18 hours, at which time TLC analysis (10% EtOAc / isohexane) indicated that the starting material was completely consumed. The reaction was diluted with water and EtOAc and the phases were separated. The aqueous phase was back-extracted with EtOAc (2 times) and the combined organic phases were washed with brine (2 times), passed through a phase separator cartridge and concentrated directly onto silica for elution with neat isohexane to 25% EtOAc / isohexane, purified by column chromatography to give the title compound (9.27 g, 35.1 mmol) as a white solid.

[0385] Step 4: Synthesis of 1,1,4,4-tetramethyl-N-(pivaloyloxy)-1,2,3,4-tetrahydrobenzo[b][1,4]disilane-6-carboxamide

[0386]

[0387] 1,1,4,4-Tetramethyl-1,2,3,4-tetrahydrobenzo[b][1,4]disilane-6-carboxylic acid 5 (9.27 g, 35.1 mmol) was dissolved in THF (350 mL) and the solution was cooled to 0°C. 2,4,6-Trioxy-2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphanin (T3P, 50% in EtOAc, 45.9 mL, 77 mmol) was added dropwise over 5 minutes and the reaction was stirred at 25°C for 90 minutes, followed by the addition of DIPEA (36.6 mL, 210 mmol) and trifluoromethanesulfonic acid O-pivaloylhydroxylamine 12 (10.30 g, 38.6 mmol). The reaction was stirred for 20 hours, at which time TLC analysis indicated complete consumption of the starting material. The reaction was diluted with water and EtOAc and the layers were separated. The aqueous phase was back extracted with EtOAc (1 x) and the combined organic extracts were washed with NaHCO (saturated aqueous solution, 1 x) and brine (saturated, 1 x) before passing through a phase separator and concentrating directly onto silica. Purification by column chromatography, eluting with neat isohexane to 10% EtOAc to 25% EtOAc / isohexane, gave the title compound (7.53 g, 95% purity, 19.67 mmol) as a waxy yellow solid.

[0388] Step 5: Synthesis of 1,1,4,4-tetramethyl-2,3,4,7-tetrahydro-[1,4]disilazo[2,3-g]isoquinolin-6(1H)-one 8

[0389]

[0390] 1,1,4,4-Tetramethyl-N-(pivaloyloxy)-1,2,3,4-tetrahydrobenzo[b][1,4]disilane-6-carboxamide 6 (7.53 g, 19.67 mmol), vinyl acetate (2.72 mL, 29.5 mmol), CsOAc (1.13 g, 5.90 mmol), and dichloro(pentamethylcyclopentadienyl)rhodium(II) dimer (0.13 g, 0.20 mmol) were combined and dissolved in MeOH. The reaction was evacuated / backfilled with nitrogen until reflux (3 times) and then heated at 45 ° C for 21 hours, at which time TLC analysis indicated complete consumption of the starting material. The reaction was concentrated directly onto silica and purified by column chromatography eluting with neat isohexane to 25% to 50% EtOAc / isohexane to give the title compound (3.49 g, 12.1 mmol) as a yellow solid.

[0391] Step 6: Synthesis of 6-chloro-1,1,4,4-tetramethyl-1,2,3,4-tetrahydro-[1,4]disilano[2,3-g]isoquinoline 9

[0392]

[0393] 1,1,4,4-Tetramethyl-2,3,4,7-tetrahydro-[1,4]disilano[2,3-g]isoquinolin-6(1H)-one 8 (3.49 g, 12.1 mmol) was dissolved in POCl (11.4 mL, 122 mmol) at 25°C and EtN (1.7 mL, 12.1 mmol) was added. The reaction mixture was sparged with nitrogen for 5 minutes, then heated to 85°C and stirred at this temperature for 75 minutes. The reaction was concentrated in vacuo and the crude product was combined with crude material from another reaction running simultaneously (2.3 g, 8.0 mmol). The combined crude material was dissolved in EtOAc (200 mL) and water (200 mL) was added. The phases were separated and the aqueous phase was back-extracted with EtOAc (2 x 100 mL). The combined organic phases were washed with brine (2 x 100 mL) and passed through a phase separator cartridge before being concentrated directly onto silica. Purification by column chromatography eluting with neat isohexane to 10% EtOAc / isohexane afforded the title compound as an orange oil (5.56 g, 18.2 mmol, 91% combined yield).

[0394] Step 7: Synthesis of 6-(3,5-dimethylphenyl)-1,1,4,4-tetramethyl-1,2,3,4-tetrahydro-[1,4]disilazo[2,3-g]isoquinoline

[0395]

[0396] 6-Chloro-1,1,4,4-tetramethyl-1,2,3,4-tetrahydro-[1,4]disilano[2,3-g]isoquinoline 9 (5.56 g, 18.2 mmol), (3,5-dimethylphenyl)boronic acid (3.27 g, 21.8 mmol), tetrakis(triphenylphosphine)palladium (1.05 g, 0.91 mmol), and KCO (10.05 g, 72.7 mmol) were combined and dissolved in THF (60 mL) and water (60 mL). The reaction mixture was sparged with nitrogen for 15 minutes, followed by vacuum-nitrogen backfill until reflux (5 times). The reaction was heated to 80° C. and stirred at this temperature for 18 hours. The reaction was cooled to 25° C. and diluted with EtOAc and water. The phases were separated and the aqueous phase was back-extracted with EtOAc (1 time). The combined organic extracts were washed with brine (1 time), passed through a phase separator and concentrated directly onto silica. Purification by column chromatography eluting with neat isohexane to 5% to 10% EtOAc / isohexane gave the title compound as a pale yellow oil which was slowly recrystallized under high vacuum to a pale yellow solid (5.63 g, 15.0 mmol).

[0397]

[0398] A suspension of 6-(3,5-dimethylphenyl)-1,1,4,4-tetramethyl-1,2,3,4-tetrahydro-[1,4]disilano[2,3-g]isoquinoline (0.17 g, 0.45 mmol) and iridium(III) chloride hydrate (75 mg, 0.21 mmol) in a mixture of 2-ethoxyethanol and water was heated at 100 °C overnight to give the intermediate μ-dichloride complex (0.3 g, 72%).

[0399] The intermediate μ-dichloride complex (70 mg, 0.036 mmol), 3,7-diethylnonane-4,6-dione (46 mg, 0.215 mmol), powdered potassium carbonate (30 mg, 0.215 mmol) were added to THF and the reaction mixture was heated at 50 ° C overnight. The reaction mixture was cooled to room temperature and DIUF water (500 mL) was added. The slurry was filtered and the solvent was removed. The residue was coated on silica gel and eluted with a gradient of a mixture of dichloromethane and hexane and purified on a silica gel column to obtain the compound of the present invention (30 mg, 36% yield) as a red solid.

[0400]

[0401] A suspension of 1-(3,5-dimethylphenyl)-6-(trimethylsilyl)isoquinoline (6.53 g, 21.37 mmol, 2.2 equiv) and iridium(III) chloride hydrate (2.9 g, 9.71 mmol, 1.0 equiv) was heated at 125°C overnight to yield the intermediate μ-dichloride complex. The reaction mixture was cooled to room temperature. 3,7-diethylnonane-4,6-dione (2.06 g, 9.71 mmol, 2.0 equiv), powdered potassium carbonate (2.02 g, 14.58 mmol, 3.0 equiv) and triethyl phosphate (60 mL) were added and the reaction mixture was heated at 42°C overnight. The reaction mixture was cooled to room temperature and DIUF water (500 mL) was added. The slurry was filtered and the solid was washed with methanol (100 mL). The red solid was dissolved in dichloromethane (250 mL), adsorbed onto silica gel (100 g) and eluted with a gradient of 5 to 40% dichloromethane in hexanes. Purification on an Interchim automated chromatography system (330 g Sorbtech silica gel cartridge) gave bis[1-(3,5-dimethylphenyl)-2'-yl)-6-(trimethylsilyl)isoquinolin-1'-yl]-(3,7-diethyl-4,6-nonanedione-k2O,O')-iridium(III) (3.45 g, 35% yield, 99.5% purity) as a red solid.

[0402] The photoluminescence (PL) spectra of the compounds of the present invention and the comparative compounds are shown in Figure 3 . The PL intensity is normalized to the maximum value of the first emission peak. Both compounds present a structural emission profile. The compound of the present invention presents a maximum peak at 639 nm, where the photoluminescence quantum yield (PLQY) is 86% and the excited state decay lifetime (τ) is 1.19 μs, while the comparative compound presents a maximum peak at 636 nm, where the PLQY is 85% and τ is 1.25 μs. Although the two compounds have similar emission peak maximum wavelengths, it can be found that the intensity of the second PL peak of the compound of the present invention is lower than that of the comparative example. The wider emission spectrum, more precisely the strong contribution from the second emission peak, is the main problem in obtaining good color purity. In addition, the compound of the present invention presents a higher PLQY and a short τ. When the compound of the present invention is used as an emissive dopant in an organic electroluminescent device, it is expected that more saturated red light emission will be emitted at higher efficiency compared to the comparative compound, thereby providing improved device performance.

Claims

1. A compound selected from the group consisting of: based on the general formula Ir(L Ai-m )2(L Cj-I ) of Ir(L A1-1 )2(L C1-I ) to Ir(L A698-68 )2(L C1416-I ) and based on the general formula Ir(L Ai-m )2(L Cj-II ) of Ir(L A1-1 )2(L C1-II ) to Ir(L A698-68 )2(L C1416-II ), Among them L A is based on L Ai-11 , where for each i, R E and G are as defined in Table 1 below: where R 1 to R 10 、R 17 、R 22 、R 28 、R 32 、R 33 、R 36 、R 41 and R 42 Has the following structure: and Among them G 16 Has the following structure: Among them L C1-I To L C1416-I is based on The structure of L C1-II To L C1416-II is based on The structure of L Cj-I and L Cj-II Each L in Cj , R 201 and R 202 Each is independently defined in the following table: where R D1 to R D5 、R D7 to R D10 、R D15 to R D22 、R D38 to R D54 、R D76 to R D88 、R D137 to R D140 、R D143 to R D185 、R D193 to R D216 and R D220 to R D243 Has the following structure:

2. A compound selected from the group consisting of:

3. An organic light-emitting device (OLED), comprising: anode; cathode; and an organic layer disposed between the anode and the cathode, The organic layer comprises the compound according to claim 1 or 2.

4. The OLED according to claim 3, wherein the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran and aza-dibenzoselenophene.

5. The OLED according to claim 4, wherein the host is selected from the group consisting of: and combinations thereof.

6. A consumer product comprising an organic light-emitting device (OLED), wherein the organic light-emitting device comprises: anode; cathode; and an organic layer disposed between the anode and the cathode, The organic layer comprises the compound according to claim 1 or 2.

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