ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES
20240284778 ยท 2024-08-22
Assignee
Inventors
- Alexey Borisovich DYATKIN (Ambler, PA, US)
- Wei-Chun SHIH (Lawrenceville, NJ, US)
- Jui-Yi TSAI (Newtown, PA, US)
Cpc classification
C09K2211/185
CHEMISTRY; METALLURGY
C09K2211/1029
CHEMISTRY; METALLURGY
C09K2211/1088
CHEMISTRY; METALLURGY
International classification
Abstract
A compound including a first ligand L.sub.A of Formula I,
##STR00001##
is provided. In Formula I, moiety B is a fused polycyclic ring system; X.sup.1 to X.sup.4 are each C or N; K is a direct bond or a linker; L.sub.A is coordinated to a metal. Formulations, OLEDs, and consumer products containing such compounds are also provided.
Claims
1. A compound comprising a first ligand L.sub.A of Formula I, ##STR00172## wherein: moiety B is a fused polycyclic ring system, wherein each ring of the fused polycyclic ring system is a 5-membered or 6-membered carbocyclic or heterocyclic ring; X.sup.1 to X.sup.4 are each independently C or N; K is selected from the group consisting of a direct bond, O, S, N(R.sup.?), P(R.sup.?), B(R.sup.?), C(R.sup.?)(R.sup.?), and Si(R.sup.?)(R.sup.?); L.sub.A is coordinated to a metal M; M may be coordinated to other ligands; L.sub.A may be joined with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand; one of the following three conditions is true: (1) at least one of R.sup.A or R.sup.B comprises a silyl group, and moiety B comprises four or more fused rings, (2) at least one R.sup.A has a structure of Formula II, ##STR00173## and at least one of R.sup.A or R.sup.B comprises a silyl group, wherein if the at least one of R.sup.A that is Formula II is joined to X.sup.3 and K is a direct bond, then at least one R.sup.C is not H, and (3) at least one R.sup.B comprises a silyl group and at least one R.sup.A comprises a cyclic group or a silyl group; wherein each of R.sup.A, R.sup.B, and R.sup.C independently represents mono to the maximum allowable substitutions, or no substitutions; each R.sup.A, R.sup.B, R.sup.C, R.sup.?, and R.sup.? is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; and any two R.sup.A, R.sup.B, R.sup.C, R.sup.?, and R.sup.? may be joined or fused to form a ring.
2. The compound of claim 1, wherein each R.sup.A, R.sup.B, R.sup.C, R.sup.?, and R.sup.? is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
3. The compound of claim 1, wherein moiety B comprises at least four fused rings; and/or wherein at least one R.sup.A comprises a silyl group; and/or wherein at least one R.sup.B comprises a silyl group.
4. The compound of claim 1, wherein moiety B is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole derived carbene, aza-benzimidazole derived carbene, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanathrene, anthracene, aza-antracene, phenanthridine, fluorene, and aza-fluorene.
5. The compound of claim 1, wherein each of X.sup.1 to X.sup.4 is C or wherein at least one of X.sup.1 to X.sup.4 is N; and/or wherein K is a direct bond, O or S; and/or wherein the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu; and/or wherein at least one R.sup.A comprises a cyclic group or a silyl group; and/or wherein at least one R.sup.B comprises a silyl group; and/or wherein L.sub.A is partially deuterated.
6. The compound of claim 1, two adjacent ones of X.sup.1 to X.sup.4 are C and the adjacent R.sup.A are joined or fused to form a ring; and/or wherein at least one additional R.sup.A comprises a moiety selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, partially or fully deuterated variants thereof, F, and silyl.
7. The compound of claim 1, wherein at least one R.sup.A has a structure of Formula II, ##STR00174## and/or wherein the R.sup.A bonded to X.sup.3 has a structure of Formula II, K is a direct bond, and at least one R.sup.C is not H.
8. The compound of claim 7, wherein the R.sup.C bonded to at least one of X.sup.5 or X.sup.9 is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; and/or wherein the R.sup.C bonded to X.sup.7 is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; and/or wherein two adjacent ones of X.sup.5 to X.sup.9 are C and the adjacent R.sup.C are joined or fused to form a ring.
9. The compound of claim 1, wherein the ligand L.sub.A is selected from the group consisting of: ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## wherein: X is Cor N; each of Y.sup.A and Y.sup.B is independently selected from the group consisting of BR.sub.e, BR.sub.eR.sub.f, NR.sub.e, PR.sub.e, P(O)R.sub.e, O, S, Se, C?O, C?S, C?Se, C?NR.sub.e, C?CR.sub.eR.sub.f, S?O, SO.sub.2, CR.sub.eR.sub.f, SIR.sub.eR.sub.f, and GeR.sub.eR.sub.f; each of R.sup.AA, R.sup.BB, and R.sup.CC; independently represents mono to the maximum allowable substitutions, or no substitutions; each R.sub.e, R.sub.f, R.sup.AA, R.sup.BB, R.sup.CC and R.sup.Si is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; and R.sup.3 is a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; with the proviso that R.sup.Si comprises a silyl moiety; and any two R.sup.A, R.sup.B, R.sup.C, R.sup.?, and R.sup.? may be joined or fused to form a ring.
10. The compound of claim 1, wherein the ligand L.sub.A is selected from the group consisting of: ##STR00188## ##STR00189## ##STR00190## ##STR00191## ##STR00192## ##STR00193## ##STR00194## ##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205## wherein: X is Cor N; each of Y.sup.A and Y.sup.B is independently selected from the group consisting of BR.sub.e, BR.sub.eR.sub.f, NR.sub.e, PR.sub.e, P(O)R.sub.e, O, S, Se, C?O, C?S, C?Se, C?NR.sub.e, C?CR.sub.eR.sub.f, S?O, SO.sub.2, CR.sub.eR.sub.f, SiR.sub.eR.sub.f, and GeR.sub.eR.sub.f; each of R.sup.AA, R.sup.BB, and R.sup.CC independently represents mono to the maximum allowable substitutions, or no substitutions; each R.sub.e, R.sub.f, R.sup.AA, R.sup.BB, R.sup.CC, and R.sup.Si is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; and R.sup.3 is a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; with the proviso that R.sup.Si comprises a silyl moiety; and any two R.sup.A, R.sup.B, R.sup.C, R.sup.?, and R.sup.? may be joined or fused to form a ring.
11. The compound of claim 1, wherein the ligand L.sub.A is selected from the group consisting of L.sub.Ai, and L.sub.AwR.sup.m)(R.sup.n)(R.sup.o)(R.sup.p)(T), wherein i is an integer from 1 to 90, w is an integer from 1 to 62, each) L.sub.AwR.sup.m)(R.sup.n)(R.sup.o)(R.sup.p)(T) is defined as follows: TABLE-US-00002 Compound Structure of compound Compound Structure of compound L.sub.A1(R.sup.m)(R.sup.n) (R.sup.o)(R.sup.p)(T), wherein L.sub.A1(R1)(R1) (R1)(R1)(T1) to L.sub.A1(R115) (R115)(R115) (R115)T(20), have the structure
12. The compound of claim 1, wherein the compound has a formula of M(L.sub.A).sub.p(L.sub.B).sub.q(L.sub.C).sub.r wherein L.sub.B and L.sub.C are each a bidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M.
13. The compound of claim 12, wherein the compound has a formula selected from the group consisting of Ir(L.sub.A).sub.3, Ir(L.sub.A)(L.sub.B).sub.2, Ir(L.sub.A).sub.2(L.sub.B), Ir(L.sub.A)(L.sub.C), and Ir(L.sub.A)(L.sub.B)(L.sub.C); and wherein L.sub.A, L.sub.B, and L.sub.C are different from each other; or a formula of Pt(L.sub.A)(L.sub.B); and wherein L.sub.A and L.sub.B can be same or different.
14. The compound of claim 12, wherein L.sub.B and L.sub.C are each independently selected from the group consisting of: ##STR00309## ##STR00310## ##STR00311## ##STR00312## ##STR00313## wherein: T is selected from the group consisting of B, Al, Ga, and In; K.sup.1 is selected from the group consisting of a single bond, O, S, NR.sub.e, PR.sub.e, BR.sub.e, CR.sub.eR.sub.f, and SiR.sub.eR.sub.f; each of Y.sup.1 to Y.sup.13 is independently selected from the group consisting of C and N; Y is selected from the group consisting of BR.sub.e, BR.sub.eR.sub.f, NR.sub.e, PR.sub.e, P(O)R.sub.e, O, S, Se, C?O, C?S, C?Se, C?NR.sub.e, C?CR.sub.eR.sub.f, S?O, SO.sub.2, CR.sub.eR.sub.f, SiR.sub.eR.sub.f, and GeR.sub.eR.sub.f; R.sub.e and R.sub.f can be fused or joined to form a ring; each R.sub.a, R.sub.b, R.sub.c, and R.sub.d independently represents from mono to the maximum allowed number of substitutions, or no substitution; each of R.sub.a1, R.sub.b1, R.sub.c1, R.sub.d1, R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e, and R.sub.f is independently a hydrogen or a subsituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thercof; and any two substituents of R.sub.a1, R.sub.b1, R.sub.c1, R.sub.d1, R.sub.1, R.sub.b, R.sub.c, and R.sub.d can be fused or joined to form a ring or form a multidentate ligand.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0019]
[0020]
DETAILED DESCRIPTION
A. Terminology
[0021] Unless otherwise specified, the below terms used herein are defined as follows:
[0022] As used herein, the term organic includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. Small molecule refers to any organic material that is not a polymer, and small molecules may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the small molecule class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a small molecule, and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
[0023] As used herein, top means furthest away from the substrate, while bottom means closest to the substrate. Where a first layer is described as disposed over a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is in contact with the second layer. For example, a cathode may be described as disposed over an anode, even though there are various organic layers in between.
[0024] As used herein, solution processable means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
[0025] A ligand may be referred to as photoactive when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as ancillary when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
[0026] As used herein, and as would be generally understood by one skilled in the art, a first Highest Occupied Molecular Orbital (HOMO) or Lowest Unoccupied Molecular Orbital (LUMO) energy level is greater than or higher than a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A higher HOMO or LUMO energy level appears closer to the top of such a diagram than a lower HOMO or LUMO energy level.
[0027] As used herein, and as would be generally understood by one skilled in the art, a first work function is greater than or higher than a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a higher work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a higher work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
[0028] The terms halo, halogen, and halide are used interchangeably and refer to fluorine, chlorine. bromine, and iodine.
[0029] The term acyl refers to a substituted carbonyl radical (C(O)R.sub.s).
[0030] The term ester refers to a substituted oxycarbonyl (OC(O)R.sub.s or C(O)OR.sub.s) radical.
[0031] The term ether refers to an OR.sub.s radical.
[0032] The terms sulfanyl or thio-ether are used interchangeably and refer to a SR.sub.s radical.
[0033] The term selenyl refers to a SeR.sub.s radical.
[0034] The term sulfinyl refers to a S(O)R.sub.s radical.
[0035] The term sulfonyl refers to a SO.sub.2R.sub.s radical.
[0036] The term phosphino refers to a P(R.sub.s).sub.2 radical, wherein each R.sub.s can be same or different.
[0037] The term silyl refers to a Si(R.sub.s).sub.3 radical, wherein each R.sub.s can be same or different.
[0038] The term germyl refers to a Ge(R.sub.s).sub.3 radical, wherein each Rs can be same or different.
[0039] The term boryl refers to a B(R.sub.s).sub.2 radical or its Lewis adduct B(R.sub.s).sub.3 radical, wherein R.sub.s can be same or different.
[0040] In each of the above, R.sub.s can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combination thereof. Preferred R.sub.s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof.
[0041] The term alkyl refers to and includes both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted.
[0042] The term cycloalkyl refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1 ]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.
[0043] The terms heteroalkyl or heterocycloalkyl refer to an alkyl or a cycloalkyl radical, 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. Additionally, the heteroalkyl or heterocycloalkyl group may be optionally substituted.
[0044] The term alkenyl refers to and includes both straight and branched chain alkene radicals. 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. The term heteroalkenyl as used herein refers to an alkenyl radical having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group may be optionally substituted.
[0045] The term alkynyl refers to and includes both straight and branched chain alkyne radicals. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.
[0046] The terms aralkyl or arylalkyl are used interchangeably and refer to an alkyl group that is substituted with an aryl group. Additionally, the aralkyl group may be optionally substituted.
[0047] The term heterocyclic group refers to and includes aromatic and non-aromatic cyclic radicals 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. Hetero-aromatic cyclic radicals may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted.
[0048] The term aryl refers to and includes both single-ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are fused) wherein at least one of the rings is an aromatic hydrocarbyl group, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted.
[0049] The term heteroaryl refers to and includes both single-ring aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. The heteroatoms include, but are not limited to O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Hetero-single ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic ring systems can have two or more rings in which two atoms are common to two adjoining rings (the rings are fused) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-polycyclic aromatic ring systems can have from one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.
[0050] Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and the respective aza-analogs of each thereof are of particular interest.
[0051] The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted, or independently substituted, with one or more General Substituents.
[0052] In many instances, the General Substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
[0053] In some instances, the Preferred General Substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
[0054] In some instances, the More Preferred General Substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof.
[0055] In yet other instances, the Most Preferred General Substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
[0056] The terms substituted and substitution refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R.sup.1 represents mono-substitution, then one R.sup.1 must be other than H (i.e., a substitution). Similarly, when R.sup.1 represents di-substitution, then two of R.sup.1 must be other than H. Similarly, when R.sup.1 represents zero or no substitution, R.sup.1, for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms.
[0057] As used herein, combinations thereof indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group; a halogen and alkyl can be combined to form a halogenated alkyl substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium.
[0058] 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 respective aromatic ring can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.
[0059] As used herein. deuterium refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.
[0060] It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
[0061] In some instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein. adjacent means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2,2 positions in a biphenyl, or 1,8 position in a naphthalene. as long as they can form a stable fused ring system.
B. The Compounds of the Present Disclosure
[0062] New metal complexes comprising a silyl group on the emitting ligand are disclosed. Such complexes exhibit a narrower line shape of electroluminescent (EL) spectrum than conventional emissive complexes. Emitter compounds having a narrower emission line shape is beneficial for obtaining higher efficiency in an OLED device.
[0063] In one aspect, the present disclosure provides a compound comprising a first ligand L.sub.A of Formula I,
##STR00003##
In Formula I:
[0064] moiety B is a fused polycyclic ring system, wherein each ring of the fused polycyclic ring system is a 5-membered or 6-membered carbocyclic or heterocyclic ring;
[0065] X.sup.1 to X.sup.4 are each independently C or N;
[0066] K is selected from the group consisting of a direct bond, O, S, N(R.sup.?), P(R.sup.?), B(R.sup.?), C(R.sup.?)(R.sup.?), and Si(R.sup.?)(R.sup.?);
[0067] L.sub.A is coordinated to a metal M;
[0068] M may be coordinated to other ligands;
[0069] L.sub.A may be joined with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand;
[0070] wherein each of R.sup.A and R.sup.B independently represents mono to the maximum allowable substitutions, or no substitutions;
[0071] each R.sup.A, R.sup.B, R.sup.?, and R.sup.? is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein; and
[0072] any two R.sup.A, R.sup.B, R.sup.?, and R.sup.? may be joined or fused to form a ring.
[0073] In some embodiments, at least one of R.sup.A or R.sup.B comprises a silyl group, and moiety B comprises four or more fused rings.
[0074] In some embodiments, at least one R.sup.A has a structure of Formula II,
##STR00004##
wherein R.sup.C represents mono to the maximum allowable substitutions, or no substitutions; each R.sup.C is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein; and at least one of R.sup.A or R.sup.B comprises a silyl group, wherein if the at least one of R.sup.A that is Formula II is joined to X.sup.3 and K is a direct bond, then at least one R.sup.C is not H. When at least one R.sup.A has a structure of Formula II, any two R.sup.A, R.sup.B, R.sup.C, R.sup.?, and R.sup.? may be joined or fused to form a ring.
[0075] In some embodiments, at least one R.sup.B comprises a silyl group and at least one R.sup.A comprises a cyclic group or a silyl group.
[0076] In some embodiments, at least one of R.sup.A or R.sup.B comprises a silyl group, and moiety B comprises four or more fused rings, and at least one R.sup.A has a structure of Formula II,
##STR00005##
wherein R.sup.C represents mono to the maximum allowable substitutions, or no substitutions; each R.sup.C is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein; and if the at least one of R.sup.A that is Formula II is joined to X.sup.3 and K is a direct bond, then at least one R.sup.C is not H.
[0077] In some embodiments, at least one of R.sup.A or R.sup.B comprises a silyl group, and moiety B comprises four or more fused rings, and at least one R.sup.A comprises a cyclic group.
[0078] In some embodiments, at least one R.sup.A has a structure of Formula II,
##STR00006##
wherein R.sup.C represents mono to the maximum allowable substitutions, or no substitutions; each R.sup.C is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein, and if the at least one of R.sup.A that is Formula II is joined to X.sup.3 and K is a direct bond, then at least one R.sup.C is not H, and at least one R.sup.B comprises a silyl group and at least one R.sup.A comprises a cyclic group or a silyl group.
[0079] In some embodiments, at least one of R.sup.A or R.sup.B comprises a silyl group, and moiety B comprises four or more fused rings, and at least one R.sup.A has a structure of Formula II,
##STR00007##
wherein R.sup.C represents mono to the maximum allowable substitutions, or no substitutions; each R.sup.C is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein, and if the at least one of R.sup.A that is Formula II is joined to X.sup.3 and K is a direct bond, then at least one R.sup.C is not H, and at least one R.sup.B comprises a silyl group and at least one R.sup.A comprises a cyclic group or a silyl group.
[0080] In some embodiments, at least one of the substituents adjacent to the substituent comprising a silyl group is a General Substituent defined herein. In some embodiments, both of the substituents adjacent to the substituent comprising a silyl group are independently General Substituents defined herein.
[0081] In some embodiments, at least one of the substituents adjacent to the substituent comprising a silyl group is a Preferred General Substituent defined herein. In some embodiments, both of the substituents adjacent to the substituent comprising a silyl group are independently Preferred General Substituents defined herein.
[0082] In some embodiments, each R.sup.A, R.sup.B, R.sup.C, R.sup.?, and R.sup.? is independently hydrogen or a substituent selected from the group consisting of the Preferred General Substituent defined herein. In some embodiments, each R.sup.A, R.sup.B, R.sup.C, R.sup.?, and R.sup.? is independently hydrogen or a substituent selected from the group consisting of the More Preferred General Substituent defined herein. In some embodiments, each R.sup.A, R.sup.B, R.sup.C, R.sup.?, and R.sup.? is independently hydrogen or a substituent selected from the group consisting of the Most Preferred General Substituent defined herein.
[0083] In some embodiments, moiety B comprises at least three fused rings. In some embodiments, moiety B comprises at least three fused aromatic rings.
[0084] In some embodiments, moiety B comprises at least four fused rings. In some embodiments, moiety B comprises at least four fused aromatic rings.
[0085] In some embodiments, moiety B comprises at least five fused rings. In some embodiments, moiety B comprises at least five fused aromatic rings.
[0086] In some embodiments, moiety B comprises at least one 5-membered ring. In some embodiments, moiety B includes exactly one 5-membered ring. In some embodiments, moiety B includes exactly one 5-membered ring, which is fused to the ring that is coordinated to metal M.
[0087] In some embodiments, moiety B is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole derived carbene, aza-benzimidazole derived carbene, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanathrene, anthracene, aza-antracene, phenanthridine, fluorene, and aza-fluorene.
[0088] In some embodiments, moiety B is independently a polycyclic fused ring structure. In some embodiments, moiety B is independently a polycyclic fused ring structure comprising at least three fused rings. In some embodiments, the polycyclic fused ring structure has two 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to metal M and the second 6-membered ring is fused to the 5-membered ring. In some embodiments, moiety B is independently selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and aza-variants thereof. In some such embodiments, moiety B can independently be further substituted at the ortho- or meta-position of the O, S, or Se atom by a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the aza-variants contain exactly one N atom at the 6-position (ortho to the O, S, or Se) with a substituent at the 7-position (meta to the O, S, or Se).
[0089] In some embodiments, moiety B is independently a polycyclic fused ring structure comprising at least four fused rings. In some embodiments, the polycyclic fused ring structure comprises three 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to metal M, the second 6-membered ring is fused to the 5-membered ring, and the third 6-membered ring is fused to the second 6-membered ring. In some such embodiments, the third 6-membered ring is further substituted by a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
[0090] In some embodiments, moiety B is independently a polycyclic fused ring structure comprising at least five fused rings. In some embodiments, the polycyclic fused ring structure comprises four 6-membered rings and one 5-membered ring or three 6-membered rings and two 5-membered rings. In some embodiments comprising two 5-membered rings, the 5-membered rings are fused together. In some embodiments comprising two 5-membered rings, the 5-membered rings are separated by at least one 6-membered ring. In some embodiments with one 5-membered ring, the 5-membered ring is fused to the ring coordinated to metal M, the second 6-membered ring is fused to the 5-membered ring, the third 6-membered ring is fused to the second 6-membered ring, and the fourth 6-membered ring is fused to the third 6-membered ring.
[0091] In some embodiments, moiety B is independently an aza version of the polycyclic fused rings described above. In some such embodiments, moiety B independently contains exactly one aza N atom. In some such embodiments, moiety B contains exactly two aza N atoms, which can be in one ring, or in two different rings. In some such embodiments, the ring having aza N atom is separated by at least two other rings from the metal M atom. In some such embodiments, the ring having aza N atom is separated by at least three other rings from the metal M atom. In some such embodiments, each of the ortho position of the aza N atom is substituted.
[0092] In some embodiments, each of X.sup.1 to X.sup.4 is C.
[0093] In some embodiments, at least one of X.sup.1 to X.sup.4 is N. In some embodiments, exactly one of X.sup.1 to X.sup.4 is N.
[0094] In some embodiments, K is a direct bond.
[0095] In some embodiments, K is O. In some embodiments, K is S.
[0096] In some embodiments, K is selected from the group consisting of N(R.sup.?), P(R.sup.?), and B(R.sup.?).
[0097] In some embodiments, K is selected from the group consisting of C(R.sup.?)(R.sup.?) and Si(R.sup.?)(R.sup.?).
[0098] In some embodiments, the metal M has an atomic mass of at least 40. In some embodiments, the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu.
[0099] In some embodiments, the metal M is Ir. In some embodiments, the metal M is Pt.
[0100] In some embodiments, two adjacent ones of X.sup.1 to X.sup.4 are C and the adjacent R.sup.A are joined or fused to form a ring.
[0101] In some embodiments, at least one R.sup.A is not hydrogen.
[0102] In some embodiments, at least one R.sup.A comprises a silyl group. In some embodiments, at least one R.sup.A comprises is trimethylsilyl or triphenylsilyl.
[0103] In some embodiments, at least one R.sup.A is a silyl group. In some embodiments, at least one R.sup.A is trimethylsilyl or triphenylsilyl.
[0104] In some embodiments, at least one R.sup.B is not hydrogen.
[0105] In some embodiments, at least one R.sup.B comprises a silyl group. In some embodiments, at least one R.sup.B comprises is trimethylsilyl or triphenylsilyl.
[0106] In some embodiments, at least one R.sup.B is a silyl group. In some embodiments, at least one R.sup.B is trimethylsilyl or triphenylsilyl.
[0107] In some embodiments, moiety B comprises four or more fused rings.
[0108] In some embodiments, at least one R.sup.A has a structure of Formula II,
##STR00008##
wherein R.sup.C represents mono to the maximum allowable substitutions, or no substitutions; each R.sup.C is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein. In some of such embodiments, the R.sup.A bonded to X.sup.3 has a structure of Formula II, K is a direct bond, and at least one R.sup.C is not H.
[0109] In some embodiments where at least one R.sup.A has a structure of Formula II, at least one R.sup.C is not H.
[0110] In some embodiments where at least one R.sup.A has a structure of Formula II, at least one R.sup.C comprises a silyl group. In some embodiments, at least one R.sup.C comprises trimethylsilyl.
[0111] In some embodiments where at least one R.sup.A has a structure of Formula II, the R.sup.C bonded to at least one of X.sup.5 or X.sup.9 is not H. In some embodiments where at least one R.sup.A has a structure of Formula II, the R.sup.C bonded to each of X.sup.5 and X.sup.9 is not H.
[0112] In some embodiments where at least one R.sup.A has a structure of Formula II, the R.sup.C bonded to at least one of X.sup.5 or X.sup.9 is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
[0113] In some embodiments where at least one R.sup.A has a structure of Formula II, the R.sup.C bonded to each of X.sup.5 and X.sup.9 is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
[0114] In some embodiments where at least one R.sup.A has a structure of Formula II, the R.sup.C bonded to X.sup.7 is not H.
[0115] In some embodiments where at least one R.sup.A has a structure of Formula II, the R.sup.C bonded to X.sup.7 is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
[0116] In some embodiments where at least one R.sup.A has a structure of Formula II, two adjacent ones of X.sup.5 to X.sup.9 are C and the adjacent R.sup.C are joined or fused to form a ring.
[0117] In some embodiments where at least one R.sup.A has a structure of Formula II, at least one additional R.sup.A is not H. In some embodiments where at least one R.sup.A has a structure of Formula II, at least one additional R.sup.A comprises a moiety selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, partially or fully deuterated variants thereof, F, and silyl.
[0118] In some embodiments, the silyl group of R.sup.A, R.sup.B, or R.sup.C has a structure of SiR.sup.SaR.sup.SbR.sup.Sc, where each of R.sup.Sa, R.sup.Sb, and R.sup.Sc is independently alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, or combinations thereof; and any two substituents may be joined or fused to form a ring.
[0119] In some embodiments, the silyl group of R.sup.A, R.sup.B, or R.sup.C is selected from the group consisting of the structures of the following Silyl List: SiEt.sub.3, Si(.sup.iPr).sub.3, Si(.sup.iBu).sub.3, SiPh.sub.3, Si(CD.sub.3).sub.3,
##STR00009##
wherein each R.sup.T independently represents mono to the maximum allowable substitutions, or no substitution;
[0120] each R.sup.T is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein; and
[0121] any two substituents may be joined or fused to form a ring.
[0122] In some embodiments, at least one R.sup.A comprises a cyclic group or a silyl group. In some embodiments, at least one R.sup.B comprises a silyl group. In some embodiments, at least one R.sup.B comprises a silyl group and at least one R.sup.A comprises a cyclic group or a silyl group.
[0123] In some embodiments of the compound, at least one of R.sup.A or R.sup.B is an electron-withdrawing group from LIST EWG 1 as defined herein. In some embodiments of the compound, at least one of R.sup.A or R.sup.B is an electron-withdrawing group from LIST EWG 2 as defined herein. In some embodiments of the compound, at least one of R.sup.A or R.sup.B is an electron-withdrawing group from LIST EWG 3 as defined herein. In some embodiments of the compound, at least one of R.sup.A or R.sup.B is an electron-withdrawing group from LIST EWG 4 as defined herein. In some embodiments of the compound, at least one of R.sup.A or R.sup.B is an electron-withdrawing group from LIST Pi-EWG as defined herein.
[0124] In some embodiments of the compound, one R.sup.A is an electron-withdrawing group from LIST EWG 1 as defined herein. In some embodiments of the compound, one of R.sup.A is an electron-withdrawing group from LIST EWG 2 as defined herein. In some embodiments of the compound, one of R.sup.A is an electron-withdrawing group from LIST EWG 3 as defined herein. In some embodiments of the compound, one of R.sup.A is an electron-withdrawing group from LIST EWG 4 as defined herein. In some embodiments of the compound, one of R.sup.A is an electron-withdrawing group from LIST Pi-EWG as defined herein.
[0125] In some embodiments of the compound, one R.sup.B is an electron-withdrawing group from LIST EWG 1 as defined herein. In some embodiments of the compound, one of R.sup.B is an electron-withdrawing group from LIST EWG 2 as defined herein. In some embodiments of the compound, one of R.sup.B is an electron-withdrawing group from LIST EWG 3 as defined herein. In some embodiments of the compound, one of R.sup.B is an electron-withdrawing group from LIST EWG 4 as defined herein. In some embodiments of the compound, one of R.sup.B is an electron-withdrawing group from LIST Pi-EWG as defined herein.
[0126] In some embodiments of the compound, the ligand L.sub.A comprises an electron-withdrawing group from LIST EWG 1 as defined herein. In some embodiments of the compound, the ligand L.sub.A comprises an electron-withdrawing group from LIST EWG 2 as defined herein. In some embodiments of the compound, the ligand L.sub.A comprises an electron-withdrawing group from LIST EWG 3 as defined herein. In some embodiments of the compound, the ligand L.sub.A comprises an electron-withdrawing group from LIST EWG 4 as defined herein. In some embodiments of the compound, the ligand L.sub.A comprises an electron-withdrawing group from LIST Pi-EWG as defined herein.
[0127] In some embodiments of the compound, the compound comprises an electron-withdrawing group from LIST EWG 1 as defined herein. In some embodiments of the compound, the compound comprises an electron-withdrawing group from LIST EWG 2 as defined herein. In some embodiments of the compound, the compound comprises an electron-withdrawing group from LIST EWG 3 as defined herein. In some embodiments of the compound, the compound comprises an electron-withdrawing group from LIST EWG 4 as defined herein. In some embodiments of the compound, the compound comprises an electron-withdrawing group from LIST Pi-EWG as defined herein.
[0128] In some embodiments, the electron-withdrawing groups commonly comprise one or more highly electronegative elements including but not limited to fluorine, oxygen, sulfur, nitrogen, chlorine, and bromine.
[0129] In some embodiments of the compound, the electron-withdrawing group has a Hammett constant larger than 0. In some embodiments, the electron-withdrawing group has a Hammett constant equal or larger than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1.
[0130] In some embodiments, the electron-withdrawn group is selected from the group consisting of the following structures (LIST EWG 1): F, CF.sub.3, CN, COCH.sub.3, CHO, COCF.sub.3, COOMe, COOCF.sub.3, NO.sub.2, SF.sub.3, SiF.sub.3, PF.sub.4, SF.sub.5, OCF.sub.3, SCF.sub.3, SeCF.sub.3, SOCF.sub.3, SeOCF.sub.3, SO.sub.2F, SO.sub.2CF.sub.3, SeO.sub.2CF.sub.3, OSeO.sub.2CF.sub.3, OCN, SCN, SeCN, NC, .sup.+N(R.sup.k2).sub.3, (R.sup.k2).sub.2CCN, (R.sup.k2).sub.2CCF.sub.3, CNC(CF.sub.3).sub.2, BR.sup.k3R.sup.k2, substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridoxine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,
##STR00010##
[0131] wherein each R.sup.k1 represents mono to the maximum allowable substitution, or no substitutions;
[0132] wherein Y.sup.G is selected from the group consisting of BR.sub.e, NR.sub.e, PR.sub.e, O, S, Se, C?O, S?O, SO.sub.2, CR.sub.eR.sub.f, SiR.sub.eR.sub.f, and GeR.sub.eR.sub.f; and
[0133] wherein each of R.sup.k1, R.sup.k2, R.sup.k3, R.sub.e, and R.sub.f is independently a hydrogen or a substituent selected from the group consisting of the General Substituents defined herein.
[0134] In some embodiments, the electron-withdrawing group is selected from the group consisting of the following structures (LIST EWG 2):
##STR00011## ##STR00012## ##STR00013## ##STR00014##
[0135] In some embodiments, the electron-withdrawing group is selected from the group consisting of the following structures (LIST EWG 3):
##STR00015## ##STR00016## ##STR00017## ##STR00018##
[0136] In some embodiments, the electron-withdrawing group is selected from the group consisting of the following structures (LIST EWG 4):
##STR00019## ##STR00020## ##STR00021##
[0137] In some embodiments, the electron-withdrawing group is a ?-electron deficient electron-withdrawing group. In some embodiments, the ?-electron deficient electron-withdrawing group is selected from the group consisting of the following structures (LIST Pi-EWG): CN, COCH.sub.3, CHO, COCF.sub.3, COOMe, COOCF.sub.3, NO.sub.2, SF.sub.3, SiF.sub.3, PF.sub.4, SF.sub.5, OCF.sub.3, SCF.sub.3, SeCF.sub.3, SOCF.sub.3, SeOCF.sub.3, SO.sub.2F, SO.sub.2CF.sub.3, SeO.sub.2CF.sub.3, OSeO.sub.2CF.sub.3, OCN, SCN, SeCN, NC, .sup.+N(R.sup.k2).sub.3, BR.sup.k2R.sup.k3, substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridazine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,
##STR00022## ##STR00023##
wherein the variables are the same as previously defined.
In some embodiments, L.sub.A is partially deuterated.
[0138] In some embodiments, ligand L.sub.A is selected from the group consisting of the structures of the following LIST 1:
##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029##
wherein:
[0139] X is C or N;
[0140] each of Y.sup.A and Y.sup.B is independently selected from the group consisting of BR.sub.e, BR.sub.eR.sub.f, NR.sub.e, PR.sub.e, P(O)R.sub.e, O, S, Se, C?O, C?S, C?Se, C?NR.sub.e, C?CR.sub.eR.sub.f, S?O, SO.sub.2, CR.sub.eR.sub.f, SiR.sub.eR.sub.f, and GeR.sub.eR.sub.f;
[0141] each of R.sup.AA, R.sup.BB, and R.sup.CC independently represents mono to the maximum allowable substitutions, or no substitutions;
[0142] each R.sub.e, R.sub.f, R.sup.AA, R.sup.BB, R.sup.CC, and R.sup.Si is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein; and
[0143] R.sup.3 is a substituent selected from the group consisting of the General Substituents defined herein;
[0144] with the proviso that R.sup.Si comprises a silyl moiety; and
[0145] any two R.sup.A, R.sup.B, R.sup.C, R.sup.?, and R.sup.? may be joined or fused to form a ring.
[0146] In some embodiments with a ligand L.sub.A of LIST 1, each of Y.sup.A and Y.sup.B is independently selected from the group consisting of O, S, Se, NR.sub.e, CR.sub.eR.sub.f, and SiR.sub.eR.sub.f. In some embodiments with a ligand L.sub.A of LIST 1, each of Y.sup.A and Y.sup.B is independently S or O.
[0147] In some embodiments with a ligand L.sub.A of LIST 1, R.sup.Si is a silyl group having a structure of SiR.sup.SaR.sup.SbR.sup.Sc. In some embodiments with a ligand L.sub.A of LIST 1, R.sup.Si is a silyl group selected from the Silyl List defined herein.
[0148] In some embodiments with a ligand L.sub.A of LIST 1, R.sup.Si comprises a silyl group having a structure of SiR.sup.SaR.sup.SbR.sup.Sc. In some embodiments with a ligand L.sub.A of LIST 1, R.sup.Si comprises a silyl group selected from the Silyl List defined herein.
[0149] In some embodiments with a ligand L.sub.A of LIST 1, at least one substituent adjacent to the bond with the silyl moiety is not H. In some embodiments with a ligand L.sub.A of LIST 1, each substituent adjacent to the bond with the silyl moiety is not H.
[0150] In some embodiments where ligand L.sub.A is selected from LIST 1, at least one of R.sup.AA, R.sup.BB, or R.sup.CC is partially or fully deuterated. In some embodiments, at least one R.sup.AA is partially or fully deuterated. In some embodiments, at least one R.sup.BB is partially or fully deuterated. In some embodiments, at least one R.sup.CC is partially or fully deuterated. In some embodiments, at least one R.sub.e or R.sub.f is partially or fully deuterated.
[0151] In some embodiments where ligand L.sub.A is selected from LIST 1, at least one R.sup.AA is or comprises an electron-withdrawing group from the LIST EWG 1 as defined herein. In some embodiments, at least one R.sup.AA is or comprises an electron-withdrawing group from the LIST EWG 2 as defined herein. In some embodiments, at least one R.sup.AA is or comprises an electron-withdrawing group from the LIST EWG 3 as defined herein. In some embodiments, at least one R.sup.AA is or comprises an electron-withdrawing group from the LIST EWG 4 as defined herein. In some embodiments, at least one R.sup.AA is or comprises an electron-withdrawing group from the LIST Pi-EWG as defined herein.
[0152] In some embodiments where ligand L.sub.A is selected from LIST 1, at least one R.sup.BB is or comprises an electron-withdrawing group from the LIST EWG 1 as defined herein. In some embodiments, at least one R.sup.BB is or comprises an electron-withdrawing group from the LIST EWG 2 as defined herein. In some embodiments, at least one R.sup.BB is or comprises an electron-withdrawing group from the LIST EWG 3 as defined herein. In some embodiments, at least one R.sup.BB is or comprises an electron-withdrawing group from the LIST EWG 4 as defined herein. In some embodiments, at least one R.sup.BB is or comprises an electron-withdrawing group from the LIST Pi-EWG as defined herein.
[0153] In some embodiments where ligand L.sub.A is selected from LIST 1, at least one R.sup.CC is or comprises an electron-withdrawing group from the LIST EWG 1 as defined herein. In some embodiments, at least one R.sup.CC is or comprises an electron-withdrawing group from the LIST EWG 2 as defined herein. In some embodiments, at least one R.sup.CC is or comprises an electron-withdrawing group from the LIST EWG 3 as defined herein. In some embodiments, at least one R.sup.CC is or comprises an electron-withdrawing group from the LIST EWG 4 as defined herein. In some embodiments, at least one R.sup.CC is or comprises an electron-withdrawing group from the LIST Pi-EWG as defined herein.
[0154] In some embodiments, the ligand L.sub.A is selected from the group consisting of the structures of the following LIST 2:
##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047##
wherein:
[0155] X is C or N;
[0156] each of Y.sup.A and Y.sup.B is independently selected from the group consisting of BR.sub.e, BR.sub.eR.sub.f, NR.sub.e, PR.sub.e, P(O)R.sub.e, O, S, Se, C?O, C?S, C?Se, C?NR.sub.e, C?CR.sub.eR.sub.f, S?O, SO.sub.2, CR.sub.eR.sub.f, SiR.sub.eR.sub.f, and GeR.sub.eR.sub.f;
[0157] each of R.sup.AA, R.sup.BB, and R.sup.CC independently represents mono to the maximum allowable substitutions, or no substitutions;
[0158] each R.sub.e, R.sub.f, R.sup.AA, R.sup.BB, R.sup.CC, and R.sup.Si is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein; and
[0159] R.sup.3 is a substituent selected from the group consisting of the General Substituents defined herein;
[0160] with the proviso that R.sup.Si comprises a silyl moiety; and
[0161] any two R.sup.A, R.sup.B, R.sup.C, R.sup.?, and R.sup.? may be joined or fused to form a ring.
[0162] In some embodiments with a ligand L.sub.A of LIST 2, each of Y.sup.A and Y.sup.B is independently selected from the group consisting of O, S, Se, NR.sub.e, CR.sub.eR.sub.f, and SiR.sub.eR.sub.f. In some embodiments with a ligand L.sub.A of LIST 2, each of Y.sup.A and Y.sup.B is independently S or O. In some embodiments with a ligand L.sub.A of LIST 2, R.sup.Si comprises a silyl group having a structure of SiR.sup.SaR.sup.SbR.sup.Sc. In some embodiments with a ligand L.sub.A of LIST 2, R.sup.Si comprises a silyl group selected from the group consisting of the structures of Silyl List defined herein.
[0163] In some embodiments with a ligand L.sub.A of LIST 2, R.sup.Si is a silyl group having a structure of SiR.sup.SaR.sup.SbR.sub.Sc. In some embodiments with a ligand L.sub.A of LIST 2, R.sup.Si is a silyl group selected from the group consisting of the structures of Silyl List defined herein.
[0164] In some embodiments with a ligand L.sub.A of LIST 2, at least one substituent adjacent to the bond with the silyl moiety is not H. In some embodiments with a ligand L.sub.A of LIST 2, each substituent adjacent to the bond with the silyl moiety is not H.
[0165] In some embodiments where ligand L.sub.A is selected from LIST 2, at least one of R.sup.AA, R.sup.BB, or R.sup.CC is partially or fully deuterated. In some embodiments, at least one R.sup.AA is partially or fully deuterated. In some embodiments, at least one R.sup.BB is partially or fully deuterated. In some embodiments, at least one R.sup.CC is partially or fully deuterated. In some embodiments, at least one R.sub.e or R.sub.f is partially or fully deuterated.
[0166] In some embodiments where ligand L.sub.A is selected from LIST 2, at least one R.sup.AA is or comprises an electron-withdrawing group from the LIST EWG 1 as defined herein. In some embodiments, at least one R.sup.AA is or comprises an electron-withdrawing group from the LIST EWG 2 as defined herein. In some embodiments, at least one R.sup.AA is or comprises an electron-withdrawing group from the LIST EWG 3 as defined herein. In some embodiments, at least one R.sup.AA is or comprises an electron-withdrawing group from the LIST EWG 4 as defined herein. In some embodiments, at least one R.sup.AA is or comprises an electron-withdrawing group from the LIST Pi-EWG as defined herein.
[0167] In some embodiments where ligand L.sub.A is selected from LIST 2, at least one R.sup.BB is or comprises an electron-withdrawing group from the LIST EWG 1 as defined herein. In some embodiments, at least one R.sup.BB is or comprises an electron-withdrawing group from the LIST EWG 2 as defined herein. In some embodiments, at least one R.sup.BB is or comprises an electron-withdrawing group from the LIST EWG 3 as defined herein. In some embodiments, at least one RBB is or comprises an electron-withdrawing group from the LIST EWG 4 as defined herein. In some embodiments, at least one R.sup.BB is or comprises an electron-withdrawing group from the LIST Pi-EWG as defined herein.
[0168] In some embodiments where ligand L.sub.A is selected from LIST 2, at least one R.sup.CC is or comprises an electron-withdrawing group from the LIST EWG 1 as defined herein. In some embodiments, at least one R.sup.CC is or comprises an electron-withdrawing group from the LIST EWG 2 as defined herein. In some embodiments, at least one R.sup.CC is or comprises an electron-withdrawing group from the LIST EWG 3 as defined herein. In some embodiments, at least one R.sup.CC is or comprises an electron-withdrawing group from the LIST EWG 4 as defined herein. In some embodiments, at least one R.sup.CC is or comprises an electron-withdrawing group from the LIST Pi-EWG as defined herein.
[0169] In some embodiments, the ligand L.sub.A is selected from L.sub.AwR.sup.m)(R.sup.n)(R.sup.o)(R.sup.p)(T), wherein w is an integer from 1 to 62, and each R.sup.m, R.sup.n, R.sup.o, and R.sup.p is independently selected from the group consisting of R1 to R115; each T is selected from T1 to T20; wherein each of L.sub.A1(R1)(R1)(R1)(R1)(T1) to L.sub.A2(R115)(R115)(R115)(R115)(T20) is defined in LIST 3a below:
TABLE-US-00001 Compound Structure of compound Compound Structure of compound L.sub.A1(R.sup.m)(R.sup.n) (R.sup.o)(R.sup.p)(T), wherein L.sub.A1(R1)(R1) (R1)(R1)(T1) to L.sub.A1(R115) (R115)(R115) (R115)T(20), have the structure
wherein R.sup.1 to R.sup.140 have the following structures:
##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123##
wherein T1 to T20 have the following structures:
##STR00124## ##STR00125## ##STR00126##
[0170] In some embodiments, the ligand L.sub.A is selected from the group consisting of L.sub.Ai, wherein i is an integer from 1 to 90, and each L.sub.Ai is defined in the following LIST 3:
##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149##
[0171] In some embodiments, the compound has a formula of M(L.sub.A).sub.p(L.sub.B),(L.sub.C).sub.r wherein L.sub.B and L.sub.C are each a bidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M.
[0172] In some embodiments, the compound has a formula selected from the group consisting of Ir(L.sub.A).sub.3, Ir(L.sub.A)(L.sub.B).sub.2, Ir(L.sub.A).sub.2(L.sub.B), Ir(L.sub.A).sub.2(L.sub.C), and Ir(L.sub.A)(L.sub.B)(L.sub.C); and wherein L.sub.A, L.sub.B, and L.sub.C are different from each other.
[0173] In some embodiments, L.sub.B is a substituted or unsubstituted phenylpyridine, and L.sub.C is a substituted or unsubstituted acetylacetonate.
[0174] In some embodiments, the compound has a formula of Pt(L.sub.A)(L.sub.B); and wherein L.sub.A and L.sub.B can be same or different. In some embodiments, L.sub.A and L.sub.B are connected to form a tetradentate ligand.
[0175] In some embodiments, L.sub.B and L.sub.C are each independently selected from the group consisting of the structures of the following LIST 4:
##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154##
[0176] wherein: [0177] T is selected from the group consisting of B, Al, Ga, and In; [0178] K.sup.1 is selected from the group consisting of a single bond, O, S, NR.sub.e, PR.sub.e, BR.sub.e, CR.sub.eR.sub.f, and SiR.sub.eR.sub.f; [0179] each of Y.sup.1 to Y.sup.13 is independently selected from the group consisting of C and N; [0180] Y is selected from the group consisting of BR.sub.e, BR.sub.eR.sub.f, NR.sub.e, PR.sub.e, P(O)R.sub.e, O, S, Se, C?O, C?S, C?Se, C?NR.sub.e, C?CR.sub.eR.sub.f, S?O, SO.sub.2, CR.sub.eR.sub.f, SiR.sub.eR.sub.f, and GeR.sub.eR.sub.f; [0181] R.sub.e and R.sub.f can be fused or joined to form a ring; [0182] each R.sub.a, R.sub.b, R.sub.c, and R.sub.d independently represents from mono to the maximum allowed number of substitutions, or no substitution; [0183] each of R.sub.a1, R.sub.b1, R.sub.c1, R.sub.d1, R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e, and R.sub.f is independently a hydrogen or a subsituent selected from the group consisting of the General Substituents defined herein; and [0184] any two substituents of R.sub.a1, R.sub.b1, R.sub.c1, R.sub.d1, R.sub.a, R.sub.b, R.sub.c, and R.sub.d can be fused or joined to form a ring or form a multidentate ligand.
[0185] In some embodiments, L.sub.B and L.sub.C are each independently selected from the group consisting of the structures of the following LIST 5:
##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171##
[0186] wherein:
[0187] R.sub.a, R.sub.b, R.sub.c, R.sub.d, and R.sub.e each independently represents zero, mono, or up to a maximum allowed number of substitution to its associated ring;
[0188] R.sub.a1, R.sub.b1, R.sub.c1, R.sub.a, R.sub.b, R.sub.c, R.sub.d, and R.sub.e each independently hydrogen or a substituent selected from the group consisting of the General Substituents defined berein; and
[0189] any two substituents of R.sub.a1, R.sub.b1, R.sub.c1, R.sub.a, R.sub.b, R.sub.c, R.sub.d, and R.sup.e can be fused or joined to form a ring or form a multidentate ligand.