ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES
A compound comprising a ligand LA of Formula I, is disclosed. In Formula I, each of Z1, Z2, Z3, Z4, Z5, and Z6 is C or N; K is selected from a direct bond, O, and S; if K is O or S, then Z6 is C; ligand LA is coordinated to a metal by the dash lines; M is coordinated to at least one other ligand; L1 is an organic linker; if M is selected from Ru, Os, or Ir, then K is O or S; if M is selected from Pt, Pd, Cu, Ag, or Au, and K is a direct bond, then M forms at least one bond to oxygen or sulfur; when M is selected from Pt, Pd, Cu, Ag, or Au, and K is O or S, then L1 is selected from —CR═N—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR′NR—, —CR′═CR″CR2—, —C(═N—)—, and —C(═CR—)—.
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This application claims priority to U.S. Provisional Application No. 63/024,566, filed May 14, 2020, and U.S. Provisional Application No. 63/155,914, filed Mar. 3, 2021, the entire contents of which are incorporated by reference herein.
FIELDThe present disclosure generally relates to organometallic compounds and formulations and their various uses including as emitters in devices such as organic light emitting diodes and related electronic devices.
BACKGROUNDOpto-electronic devices that make use of organic materials are becoming increasingly desirable for various reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Alternatively, the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single emissive layer (EML) device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.
SUMMARYIn one aspect, the present disclosure provides a compound comprising a ligand LA of Formula I,
each of Z1, Z2, Z3, Z4, Z5, and Z6 is independently C or N;
K is selected from the group consisting of a direct bond, O, and S;
when K is O or S, then Z6 is C;
each of ring A1 and ring A2 is independently a 5-membered or 6-membered carbocyclic or heterocyclic rings or a multicyclic fused-ring system comprising more than one 5-membered or 6-membered carbocyclic or heterocyclic ring;
each of RA and RB is independently mono, up to a maximum allowed substitutions, or no substitution;
ligand LA is coordinated to a metal M by the two indicated dash lines;
M is selected from the group consisting of Ru, Os, Ir, Pd, Pt, Cu, Ag, and Au;
M is coordinated to at least one other ligand;
LA can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand;
L1 is an organic linker;
when M is selected from the group consisting of Ru, Os, and Ir, then K is O or S;
when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au, and K is a direct bond, then M forms at least one bond to oxygen or sulfur;
when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au, and K is O or S, then L1 is selected from the group consisting of —CR═N—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR′NR—, —CR′═CR″CR2—, —C(═N—)—, and —C(═CR—)—;
each RA, RB, R, R′, R″ is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
any two adjacent RA, RB, R, R′ and R″ can be joined or fused together to form a ring.
In another aspect, the present disclosure provides a formulation of the compound of the present disclosure.
In yet another aspect, the present disclosure provides an OLED having an organic layer comprising the compound of the present disclosure.
In yet another aspect, the present disclosure provides a consumer product comprising an OLED with an organic layer comprising the compound of the present disclosure.
Unless otherwise specified, the below terms used herein are defined as follows:
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.
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.
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.
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.
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.
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.
The terms “halo,” “halogen,” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.
The term “acyl” refers to a substituted carbonyl radical (C(O)—Rs).
The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—Rs or —C(O)—O—Rs) radical.
The term “ether” refers to an —ORs radical.
The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SR radical.
The term “sulfinyl” refers to a —S(O)—Rs radical.
The term “sulfonyl” refers to a —SO2—Rs radical.
The term “phosphino” refers to a —P(Rs)3 radical, wherein each Rs can be same or different.
The term “silyl” refers to a —Si(Rs)3 radical, wherein each Rs can be same or different.
The term “boryl” refers to a —B(Rs)2 radical or its Lewis adduct —B(Rs)3 radical, wherein Rs can be same or different.
In each of the above, Rs 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 Rs is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
In many instances, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.
In some instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boryl, aryl, heteroaryl, sulfanyl, and combinations thereof.
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.
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 R1 represents mono-substitution, then one R1 must be other than H (i.e., a substitution). Similarly, when R1 represents di-substitution, then two of R1 must be other than H. Similarly, when R1 represents zero or no substitution, R1, 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.
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.
The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H 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.
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.
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.
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 DisclosureIn one aspect, the present disclosure provides a compound comprising a ligand LA of Formula I,
In Formula I, each of Z1, Z2, Z3, Z4, Z5, and Z6 each independently C or N;
K is selected from the group consisting of a direct bond, O, and S;
when K is O or S, then Z6 is C;
each of ring A1 and ring A2 is independently a 5-membered or 6-membered carbocyclic or heterocyclic rings or a multicyclic fused-ring system comprising more than one 5-membered or 6-membered carbocyclic or heterocyclic ring;
each of RA and RB is independently mono, up to a maximum allowed substitutions, or no substitution;
ligand LA is coordinated to a metal M by the two indicated dash lines;
M is selected from the group consisting of Ru, Os, Ir, Pd, Pt, Cu, Ag, and Au;
M is coordinated to at least one other ligand;
LA can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand;
L1 is an organic linker;
when M is selected from the group consisting of Ru, Os, and Ir, then K is O or S;
when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au, and K is a direct bond, then M forms at least one bond to oxygen or sulfur;
when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au, and K is O or S, then L1 is selected from the group consisting of —CR═N—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR′NR—, —CR′═CR″CR2—, —C(═N—)—, and —C(═CR—)—;
each RA, RB, R, R′, R″ is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and
any two adjacent RA, RB, R, R′ and R″ can be joined or fused together to form a ring.
In some embodiments, each RA, RB, R, R′, R″ is independently a hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein. In some embodiments, each RA, RB, R, R′, R″ is independently a hydrogen or a substituent selected from the group consisting of the more preferred general substituents defined herein. In some embodiments, each RA, RB, R, R′, R″ is independently a hydrogen or a substituent selected from the group consisting of the most preferred general substituents defined herein.
In some embodiments, Z3 is selected from the group consisting of N and carbene carbon.
In some embodiments, Z6 is C and K is O or S. In some embodiments, Z6 is N and K is a direct bond.
In some embodiments, ring A1 is selected from the group consisting of imidazole, benzimidazole, imidazole-based carbene, benzimidazole-based carbene, pyrimidine, pyrazole, and pyridine.
In some embodiments, ring A2 is selected from the group consisting of benzene, pyridine, carbazole, benzimidazole, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, dibenzofluorene, naphthalene, tetrahydronaphthalene, phenoxazine, 9,10-dihydroacridine, anthracene, and phenanthrene.
In some embodiments, M is selected from the group consisting of Ru, Os, and Ir. In some embodiments, K is O. In some embodiments, K is S.
In some embodiments, M is selected from the group consisting of Pt, Pd, Cu, Ag, or Au, and K is a direct bond.
In some embodiments, the organic linker L1 is selected from the group consisting of —X—, —X—X′—, —XL═XL′—, and —XL═XL′—X—, where X and X′ are each independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R″, SiR′R″, and GeR′R″; and XL and XL′ are each independently selected from the group consisting of N and CR′.
In some embodiments, L1 is —X—. In some embodiments, L1 is —X—X′—. In some embodiments, L1 is —XL═XL′—. In some embodiments, L1 is —XL═XL′—X—.
In some embodiments, at least one R, R′ or R″ forms a ring with one of RA, RB, R, R′, or R″.
In some embodiments, each R, R′, and R″ is independently hydrogen or a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, and combinations thereof.
In some embodiments, M is selected from the group consisting of Pt, Pd, Cu, Ag, or Au, and K is S or O. In some such embodiments, L1 is —CR═N—. In some such embodiments, L1 is —CR′R″CR′R″—. In some such embodiments, L1 is —NR′BR′—. In some such embodiments, L1 is —CR′R″O—. In some such embodiments, L1 is —CR′R″S—. In some such embodiments, at least one R, R′ or R″ forms a ring with one of RA, RB, R, R′, or R″. In some such embodiments, each R, R′, and R″ is independently hydrogen or a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, and combinations thereof.
In some embodiments, ligand LA is selected from the group consisting of the structures of the following LIST 1:
and wherein each RA, RB, RC, R1, R2, R3, and R4 is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein.
In some embodiments, ligand LA is selected from the group consisting of the following structures, wherein the group will be collectively referred to as LA,spec: LA1-(Ri)(Rj)(Rk)(Rl), LA2-(Ri)(Rj)(Rk)(Rl), LA3-(Ri)(Rj)(Rk)(Rl), LA4-(Ri)(Rj)(Rk)(Rl), LA5-(Ri)(Rj)(Rk)(Rl), LA6-(Ri)(Rj)(Rk)(Rl), LA7-(Ri)(Rj), LA8-(Ri)(Rj), LA9-(Ri)(Rj), LA10-(Ri)(Rj), LA11-(Ri)(Rj), LA12-(Ri)(Rj), LA13-(Ri)(Rj), LA14-(Ri)(Rj), LA15-(Ri)(Rj), LA16-(Ri)(Rj), LA17-(Ri)(Rj), LA18-(Ri)(Rj), LA19-(Ri)(Rj), LA20-(Ri)(Rj), LA21-(Ri)(Rj), LA22-(Ri)(Rj), LA23-(Ri)(Rj), LA24-(Ri)(Rj), LA25-(Ri)(Rj), LA26-(Ri)(Rj), LA27-(Ri)(Rj), LA28-(Ri)(Rj), LA29-(Ri)(Rj), LA30-(Ri)(Rj), LA31-(Ri)(Rj), LA32-(Ri)(Rj), LA33-(Ri)(Rj), LA34-(Ri)(Rj), LA35-(Ri)(Rj), LA36-(Ri)(Rj), LA37-(Ri)(Rj), LA38-(Ri)(Rj), LA39-(Ri)(Rj), LA40-(Ri)(Rj), LA41-(Ri)(Rj)(Rk), LA42-(Ri)(Rj)(Rk), LA43-(Ri)(Rj), LA44-(Ri)(Rj), LA45-(Ri)(Rj), LA46-(Ri)(Rj), LA47-(Ri)(Rj), LA48-(Ri)(Rj), LA49-(Ri)(Rj), LA50-(Ri)(Rj), LA51-(Ri)(Rj)(Rk), LA52-(Ri)(Rj)(Rk), LA53-(Ri)(Rj)(Rk), LA54-(Ri)(Rj)(Rk), LA55-(Ri)(Rj)(Rk), LA56-(Ri)(Rj)(Rk), LA57-(Ri)(Rj)(Rk), LA58-(Ri)(Rj)(Rk), LA59-(Ri)(Rj)(Rk), LA60-(Ri)(Rj)(Rk), LA61-(Ri)(Rj)(Rk), LA62-(Ri)(Rj)(Rk), LA63-(Ri)(Rj)(Rk), LA64-(Ri)(Rk), LA65-(Ri), LA66-(Ri), LA67-(Ri), LA68-(Ri), LA69-(Ri), LA70-(Ri), and LA71-(Ri), wherein each of i, j, k, and l is independently an integer from 1 to 86, wherein the structure of each ligand LA in the group LA,spec is defined by the following LIST 2:
wherein Ph represents phenyl; and
wherein R1 to R86 have the structures in the following LIST 3:
In some embodiments, the ligand LA is selected from the group consisting of LA1-(R33)(R2)(R1)(R1), LA2-(R33)(R2)(R1)(R1), LA1-(R33)(R6)(R1)(R1), LA2-(R33)(R6)(R1)(R1), LA3-(R33)(R2)(R1)(R1), LA4-(R33)(R2)(R1)(R1), LA1-(R49)(R2)(R1)(R1), LA2-(R49)(R2)(R1)(R1), LA1-(R30)(R2)(R1)(R1), LA2-(R30)(R2)(R1)(R1), LA1-(R30)(R6)(R1)(R1), LA2-(R30)(R6)(R1)(R1), LA1-(R30)(R28)(R1)(R1), LA2-(R30)(R28)(R1)(R1), LA1-(R33)(R28)(R1)(R1), LA2-(R33)(R28)(R1)(R1), LA45-(R33)(R2), LA46-(R33)(R2), LA9-(R33)(R1), LA10-(R33)(R1), LA11-(R33)(R1), LA12-(R33)(R1), LA13-(R33)(R1), LA14-(R33)(R1), LA21-(R33)(R1), LA22-(R33)(R1), LA33-(R33)(R1), LA34-(R33)(R1), LA41-(R48)(R1)(R1), LA65-(R2), LA66-(R2), LA67-(R2), LA68-(R2), LA69-(R3), LA70-(R3), LA61-(R2)(R1)(R1), LA62-(R2)(R1)(R1), LA59-(R2)(R1)(R1), LA59-(R3)(R1)(R1), LA60-(R2)(R1)(R1), LA60-(R3)(R1)(R1), LA4-(R33)(R2)(R1)(R1), LA43-(R33)(R2), and LA44-(R33)(R2).
In some embodiments, the compound has a formula of M(LA)p(LB)q(LC)r wherein LB and LC 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.
In some embodiments, the compound has a formula selected from the group consisting of Ir(LA)3, Ir(LA)(LB)2, Ir(LA)2(LB), Ir(LA)2(LC), and Ir(LA)(LB)(LC); and wherein LA, LB, and LC are different from each other. In some embodiments, M is Ir, LB is a substituted or unsubstituted phenylpyridine, and LC is a substituted or unsubstituted acetylacetonate.
In some embodiments, the compound has a formula of Pt(LA)(LB); and wherein LA and LB can be same or different. In some such embodiments, LA and LB are connected to form a tetradentate ligand.
In some embodiments, LB and LC are each independently selected from the group consisting of the structures of the following LIST 4:
wherein:
T is selected from the group consisting of B, Al, Ga, and In;
each of Y1 to Y13 is independently selected from the group consisting of carbon and nitrogen;
Y′ is selected from the group consisting of BRe, NRe, PRe, O, S, Se, C═O, S═O, SO2, CReRf, SieRf, and GeReRf;
Re and Rf can be fused or joined to form a ring;
each Ra, Rb, Rc, and Rd independently represents zero, mono, or up to a maximum allowed number of substitutions to its associated ring;
each of Ra1, Rb1, Rc1, Rd1, Ra, Rb, Rc, Rd, Re and Rf is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and
any two adjacent Ra, Rb, Rc, Rd, Re and Rf can be fused or joined to form a ring or form a multidentate ligand.
In some embodiments, LB and LC are each independently selected from the group consisting of the structures of the following LIST 5:
wherein: Ra′, Rb′, Rc′, Rd′, Re′, Rf′, Rg′, and Rn′ each independently represents zero, mono, or up to a maximum allowed substitution to its associated ring; each of Ra1, Rb1, Rc1, Ra, Rb, Rc, Ra′, Rb′, Rc′, Rd′, Rf′, Rg′, and Rn′ is independently hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein; and two adjacent Ra′, Rb′, Rc′, Rd′, Re′, Rf′, Rg′, and Rn′ can be fused or joined to form a ring or form a multidentate ligand.
In some embodiments, when the compound has formula Ir(LA)3, LA is selected from the group consisting of the structures in the group LA,spec, and the compound is selected from the group consisting of Ir(LA1-(R1)(R1)(R1)(R1))3 to Ir(LA71-(R86))3. Using the nomenclature for each of the ligand LA in the group LA,spec, the group of compounds consisting of Ir(LA1-(R1)(R1)(R1)(R1))3 to Ir(LA71-(R86))3 can also be written as Ir(LA1-(R1)(R1)(R1)(R1))3 to Ir(LA1-(R86)(R86)(R86)(R86))3, Ir(LA2-(R1)(R1)(R1)(R1))3 to Ir(LA2-(R86)(R86)(R86)(R86))3, Ir(LA3-(R1)(R1)(R1)(R1))3 to Ir(LA3-(R86)(R86)(R86)(R86))3, Ir(LA4-(R1)(R1)(R1)(R1))3 to Ir(LA4-(R86)(R86)(R86)(R86))3, Ir(LA5-(R1)(R1)(R1)(R1))3 to Ir(LA5-(R86)(R86)(R86)(R86))3, Ir(LA6-(R1)(R1)(R1)(R1))3 to Ir(LA6-(R86)(R86)(R86)(R86))3, Ir(LA7-(R1)(R1))3 to Ir(LA7-(R86)(R86))3, Ir(LA8-(R1)(R1))3 to Ir(LA8-(R86)(R86))3, Ir(LA9-(R1)(R1))3 to Ir(LA9-(R86)(R86))3, Ir(LA10-(R1)(R1))3 to Ir(LA10-(R86)(R86))3, Ir(LA11-(R1)(R1))3 to Ir(LA11-(R86)(R86))3, Ir(LA12-(R1)(R1))3 to Ir(LA12-(R86)(R86))3, Ir(LA13-(R1)(R1))3 to Ir(LA13-(R86)(R86))3, Ir(LA14-(R1)(R1))3 to Ir(LA14-(R86)(R86))3, Ir(LA15-(R1)(R1))3 to Ir(LA15-(R86)(R86))3, Ir(LA16-(R1)(R1))3 to Ir(LA16-(R86)(R86))3, Ir(LA17-(R1)(R1))3 to Ir(LA17-(R86)(R86))3, Ir(LA18-(R1)(R1))3 to Ir(LA18-(R86)(R86))3, Ir(LA19-(R1)(R1))3 to Ir(LA19-(R86)(R86))3, Ir(LA20-(R1)(R1))3 to Ir(LA20-(R86)(R86))3, Ir(LA21-(R1)(R1))3 to Ir(LA21-(R86)(R86))3, Ir(LA22-(R1)(R1))3 to Ir(LA22-(R86)(R86))3, Ir(LA23-(R1)(R1))3 to Ir(LA23-(R86)(R86))3, Ir(LA24-(R1)(R1))3 to Ir(LA24-(R86)(R86))3, Ir(LA25-(R1)(R1)3 to Ir(LA25-(R86)(R86)3, Ir(LA26-(R1)(R1))3 to Ir(LA26-(R86)(R86))3, Ir(LA27-(R1)(R1))3 to Ir(LA27-(R86)(R86))3, Ir(LA28-(R1)(R1))3 to Ir(LA28-(R86)(R86))3, Ir(LA29-(R1)(R1))3 to Ir(LA29-(R86)(R86))3, Ir(LA30-(R1)(R1))3 to Ir(LA30-(R86)(R86))3, Ir(LA31-(R1)(R1))3 to Ir(LA31-(R86)(R86))3, Ir(LA32-(R1)(R1))3 to Ir(LA32-(R86)(R86))3, Ir(LA33-(R1)(R1))3 to Ir(LA33-(R86)(R86))3, Ir(LA34-(R1)(R1))3 to Ir(LA34-(R86)(R86))3, Ir(LA35-(R1)(R1))3 to Ir(LA35-(R86)(R86))3, Ir(LA36-(R1)(R1))3 to Ir(LA36-(R86)(R86))3, Ir(LA37-(R1)(R1))3 to Ir(LA37-(R86)(R86))3, Ir(LA38-(R1)(R1))3 to Ir(LA38-(R86)(R86))3, Ir(LA39-(R1)(R1))3 to Ir(LA39-(R86)(R86))3, Ir(LA40-(R1)(R1))3 to Ir(LA40-(R86)(R86))3, Ir(LA41-(R1)(R1)(R1))3 to Ir(LA41-(R86)(R86)(R86))3, Ir(LA42-(R1)(R1)(R1))3 to Ir(LA42-(R86)(R86)(R86))3, Ir(LA43-(R1)(R1))3 to Ir(LA43-(R86)(R86))3, Ir(LA44-(R1)(R1))3 to Ir(LA44-(R86)(R86))3, Ir(LA45-(R1)(R1))3 to Ir(LA45-(R86)(R86))3, Ir(LA46-(R1)(R1))3 to Ir(LA46-(R86)(R86))3, Ir(LA47-(R1)(R1))3 to Ir(LA47-(R86)(R86))3, Ir(LA48-(R1)(R1))3 to Ir(LA48-(R86)(R86))3, Ir(LA49-(R1)(R1))3 to Ir(LA49-(R86)(R86))3, Ir(LA50-(R1)(R1))3 to Ir(LA50-(R86)(R86))3, Ir(LA51-(R1)(R1)(R1))3 to Ir(LA51-(R86)(R86)(R86))3, Ir(LA52-(R1)(R1)(R1))3 to Ir(LA52-(R86)(R86)(R86))3, Ir(LA53-(R1)(R1)(R1))3 to Ir(LA53-(R86)(R86)(R86))3, Ir(LA54-(R1)(R1)(R1))3 to Ir(LA54-(R86)(R86)(R86))3, Ir(LA55-(R1)(R1)(R1))3 to Ir(LA55-(R86)(R86)(R86))3, Ir(LA56-(R1)(R1)(R1))3 to Ir(LA56-(R86)(R86)(R86))3, Ir(LA57-(R1)(R1)(R1))3 to Ir(LA57-(R86)(R86)(R86))3, Ir(LA58-(R1)(R1)(R1))3 to Ir(LA58-(R86)(R86)(R86))3, Ir(LA59-(R1)(R1)(R1))3 to Ir(LA59-(R86)(R86)(R86))3, Ir(LA60-(R1)(R1)(R1))3 to Ir(LA60-(R86)(R86)(R86))3, Ir(LA61-(R1)(R1)(R1))3 to Ir(LA61-(R86)(R86)(R86))3, Ir(LA62-(R1)(R1)(R1))3 to Ir(LA62-(R86)(R86)(R86))3, Ir(LA63-(R1)(R1)(R1))3 to Ir(LA63-(R86)(R86)(R86))3, Ir(LA64-(R1)(R1)(R1))3 to Ir(LA64-(R86)(R86)(R86))3, Ir(LA65-(R1))3 to Ir(LA65-(R86))3, Ir(LA66-(R1))3 to Ir(LA66-(R86))3, Ir(LA67-(R1))3 to Ir(LA67-(R86))3, Ir(LA68-(R1))3 to Ir(LA68-(R86))3, Ir(LA69-(R1))3 to Ir(LA69-(R86))3, Ir(LA70-(R1))3 to Ir(LA70-(R86))3, and Ir(LA71-(R1))3 to Ir(LA71-(R86))3.
In some embodiments, when the compound has formula Ir(LA)(LBk)2, LA is selected from the group consisting of the structures of LA,spec; where k is an integer from 1 to 540; and the compound is selected from the group consisting of Ir(LA1-(R1)(R1)(R1)(R1)(LB1)2 to Ir(LA71-(R86))(LB540)2, wherein each of the compounds in the group consisting of Ir(LA1-(R1)(R1)(R1)(R1)(LB1)2 to Ir(LA71-(R86)(LB540)2 can be written using the nomenclature for each of the ligand LA in the group LA,spec, in the similar manner shown above for the compound of formula Ir(LA)3.
In some embodiments, when the compound has formula Ir(LA)2(LBk), LA is selected from the group consisting of the structures of LA,spec; where k is an integer from 1 to 540; and the compound is selected from the group consisting of Ir(LA1-(R1)(R1)(R1)(R1))2(LB1) to Ir(LA71-(R86))2(LB540), wherein each of the compounds in the group consisting of Ir(LA1-(R1)(R1)(R1)(R1))2(LB1) to Ir(LA71-(R86))2(LB540) can be written using the nomenclature for each of the ligand LA in the group LA,spec, in the similar manner shown above for the compound of formula Ir(LA)3.
In some embodiments, when the compound has formula Ir(LA)2(LCj-1), LA is selected from the group consisting of the structures of LA,spec; where j is an integer from 1 to 1416; and the compound is selected from the group consisting of Ir(LA1-(R1)(R1)(R1)(R1))2(LC1-I) to Ir(LA71-(R86)(LC1416-I), wherein each of the compounds in the group consisting of Ir(LA1-(R1)(R1)(R1)(R1))2(LC1-I) to Ir(LA71-(R86)(LC1416-I) can be written using the nomenclature for each of the ligand LA in the group LA,spec, in the similar manner shown above for the compound of formula Ir(LA)3.
In some embodiments, when the compound has formula Ir(LA)2(LCj-II), LA is selected from the group consisting of the structures of LA,spec; where j is an integer from 1 to 1416; and the compound is selected from the group consisting of Ir(LA1-(R1)(R1)(R1)(R1))2(LC1-II) to Ir(LA71-(R86)(LC1416-II), wherein each of the compounds in the group consisting of Ir(LA1-(R1)(R1)(R1)(R1))2(LC1-II) to Ir(LA71-(R86)(LC1416-II) can be written using the nomenclature for each of the ligand LA in the group LA,spec, in the similar manner shown above for the compound of formula Ir(LA)3.
In each of the embodiments of the compound disclosed herein where the compound includes one or more ligand LBk where k is an integer from 1 to 540, each LBk has the structure defined in the following LIST 6:
In each of the embodiments of the compounds disclosed herein where the compound includes one or more ligands LCj-I and/or LCj-II where j is an integer from 1 to 1416, each LCj-I has a structure based on formula
and
each LCj-II has a structure based on formula
wherein for each LG in LCj in LCj-I and LCj-II, R201 and R20 are each independently defined in the following LIST 7:
wherein RD1 to RD246 have the structures in the following LIST 8:
In some embodiments, the compound has the formula Ir(LA)(LBk)2 or Ir(LA)2(LBk), wherein the compound is selected from the group consisting of only those compounds having one of the following structures for the LBk ligand: LB1, LB2, LB18, LB28, LB38, LB108, LB118, LB122, LB124, LB126, LB128, LB130, LB32, LB134, LB136, LB138, LB140, LB142, LB144, LB156, LB58, LB160, LB162, LB164, LB168, LB172, LB175, LB204, LB206, LB214, LB216, LB218, LB220, LB222, LB231, LB233, LB235, LB237, LB240, LB242, LB244, LB246, LB248, LB250, LB252, LB254, LB256, LB258, LB260, LB262, LB263, LB264, LB265, LB266, LB267, LB268, LB269, and LB270.
In some embodiments, the compound has the formula Ir(LA)(LBk)2 or Ir(LA)2(LBk), wherein the compound is selected from the group consisting of only those compounds having one of the following structures for the LBk ligand: LB1, LB2, LB18, LB28, LB38, LB108, LB118, LB122, LB124, LB126, LB128, LB132, LB136, LB138, LB142, LB156, LB162, LB204, LB206, LB214, LB216, LB218, LB220, LB231, LB233, LB37, LB265, LB266, LB267, LB268, LB269, and LB270.
In some embodiments, LCj-I and LCj-II are each independently selected from only those structures in their corresponding group whose corresponding R201 and R202 are one of the following structures: RD1, RD3, RD4, RD5, RD9, RD10, RD17, RD18, RD20, RD22, RD37, RD40, RD41, RD42, RD43, RD48, RD49, RD50, RD54, RD55, RD58, RD59, RD78, RD79, RD81, RD87, RD88, RD89, RD93, RD116, RD117, RD118, RD119, RD120, RD133, RD134, RD135, RD136, RD143, RD144, RD145, RD146, RD147, RD149, RD151, RD154, RD155, RD156, RD175, RD1190, RD193, RD200, RD201, RD206, RD210, RD214, RD215, RD216, RD218, RD219, RD220, RD227, RD237, RD241, RD242, RD245, and RD246.
In some embodiments, LCj-I and LCj-II are each independently selected from only those structures in their corresponding group whose corresponding R201 and R22 are one of selected from the following structures RD1, RD3, RD4, RD5, RD9, RD10, RD17, RD22, RD43, RD50, RD78, RD116, RD118, RD133, RD134, RD135, RD136, RD143, RD144, RD145, RD146, RD149, RD151, RD154, RD155, RD190, RD193, RD200, RD201, RD206, RD210, RD214, RD215, RD216, RD218, RD219, RD220, RD227, RD237, RD241, RD242, RD245, and RD246.
In some embodiments, the compound has the formula Ir(LA)2(LCj-I), and the compound is selected from the group consisting of only those compounds having one of the structures of the following LIST 9 for the LCj-I ligand:
In some embodiments, the compound is selected from the group consisting of the structures of the following LIST 10:
In some embodiments, the compound has a structure of Formula II,
In the structure of Formula II:
M1 is Pd or Pt;
rings E and F are each independently a 5-membered or 6-membered carbocyclic or heterocyclic ring;
Z and Z′ are each independently C or N;
K1 and K2 are each independently selected from the group consisting of a direct bond, O, and S, wherein at least one of K1 and K2 is a direct bond;
L1 is an organic linker;
L2, L3 and L4 are each independently selected from the group consisting of a single bond, absent a bond, O, S, CR′R″, SiR′R″, BR′, and NR′, wherein at least one of L2, L3 and L4 is present;
X3 and X4 are each independently C or N;
RE and RF each independently represents zero, mono, or up to a maximum allowed substitution to its associated ring;
each of R′, R″, RE, and RF is independently a hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein; and
any two adjacent RA, RB, R, R′, R″ RE, and RF can be joined or fused together to form a ring.
In some embodiments of Formula II, ring E and ring F are both 6-membered aromatic rings.
In some embodiments of Formula II, ring F is a 5-membered or 6-membered heteroaromatic ring.
In some embodiments of Formula II, L1 is O or CR′R″.
In some embodiments of Formula II, Z′ is N and Z is C. In some embodiments of Formula II, Z′ is C and Z is N.
In some embodiments of Formula II, L2 is a direct bond. In some embodiments of Formula II, L2 is NR′.
In some embodiments of Formula II, K1 and K2 are both direct bonds.
In some embodiments of Formula II, X3 and X4 are both C.
In some embodiments, the compound is selected from the group consisting of the structures in the following LIST 11:
wherein: L1a is selected from the group of —CR═N—, —CR′R″CR′R″—, —NR′BR—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR″NR—, —CR′═CR″CR2—, —C(═CR—)—, and —C(═N—)—; L1b is selected from the group of —CR═N—, —CR2—, —CR═CR′—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR″NR—, —CR′═CR″CR2—, —C(═CR—)—, and —C(═N—)—; RY are each selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof; each RG is independently a hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein; and any two RA, RB, RE, RF, RG, RY, R, R′ and R″ can be joined together to form a ring.
In some embodiments, the compound is selected from the group consisting of the structures in the following LIST 12:
In another aspect, the present disclosure also provides an OLED device comprising a first organic layer that contains a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the OLED comprises an anode, a cathode, and a first organic layer disposed between the anode and the cathode. The first organic layer can comprise a compound comprising a ligand LA of Formula I described herein.
In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan, wherein any substituent in the host is an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡CCnH2n+1, Ar1, Ar1—Ar2, CnH2n+1—Ar1, or no substitution, wherein n is from 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.
In some embodiments, the organic layer may further comprise a host, wherein host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).
In some embodiments, the host may be selected from the HOST Group consisting of:
and combinations thereof.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.
In some embodiments, the compound as described herein may be a sensitizer; wherein the device may further comprise an acceptor; and wherein the acceptor may be selected from the group consisting of fluorescent emitter, delayed fluorescence emitter, and combination thereof.
In yet another aspect, the OLED of the present disclosure may also comprise an emissive region containing a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the emissive region can comprise a compound comprising a ligand LA of Formula I described herein.
In some embodiments, at least one of the anode, the cathode, or anew layer disposed over 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 mode of surface plasmon polariton. The enhancement layer is provided no more than a threshold distance away from the organic emissive layer, wherein the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer and the threshold distance is where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed over the enhancement layer on the opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on opposite side of the emissive layer from the enhancement layer but still outcouples energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters the energy from the surface plasmon polaritons. In some embodiments this energy is scattered as photons to free space. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device such as but not limited to the organic waveguide mode, the substrate mode, or another waveguiding mode. If energy is scattered to the non-free space mode of the OLED other outcoupling schemes could be incorporated to extract that energy to free space. In some embodiments, one or more intervening layer can be disposed between the enhancement layer and the outcoupling layer. The examples for interventing layer(s) can be dielectric materials, including organic, inorganic, perovskites, oxides, and may include stacks and/or mixtures of these materials.
The enhancement layer modifies the effective properties of the medium in which the emitter material resides resulting in any or all of the following: a decreased rate of emission, a modification of emission line-shape, a change in emission intensity with angle, a change in the stability of the emitter material, a change in the efficiency of the OLED, and reduced efficiency roll-off of the OLED device. Placement of the enhancement layer on the cathode side, anode side, or on both sides results in OLED devices which take advantage of any of the above-mentioned effects. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLEDs according to the present disclosure may include any of the other functional layers often found in OLEDs.
The enhancement layer can be comprised of plasmonic materials, optically active metamaterials, or hyperbolic metamaterials. 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 includes at least one metal. In such embodiments the metal may include at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca alloys or mixtures of these materials, and stacks of these materials. In general, a metamaterial is a medium composed of different materials where the medium as a whole acts differently than the sum of its material parts. In particular, we define optically active metamaterials as materials which have both negative permittivity and negative permeability. Hyperbolic metamaterials, on the other hand, are anisotropic media in which the permittivity or permeability are of different sign for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly distinguished from many other photonic structures such as Distributed Bragg Reflectors (“DBRs”) in that the medium should appear uniform in the direction of propagation on the length scale of the wavelength of light. Using terminology that one skilled in the art can understand: the dielectric constant of the metamaterials in the direction of propagation can be described with the effective medium approximation. Plasmonic materials and metamaterials provide methods for controlling the propagation of light that can enhance OLED performance in a number of ways.
In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the wavelength-sized features and the sub-wavelength-sized features have sharp edges.
In some embodiments, the outcoupling layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the outcoupling layer may be composed of a plurality of nanoparticles and in other embodiments the outcoupling layer is composed of a plurality of nanoparticles disposed over a material. In these embodiments the outcoupling may be tunable by at least one of varying a size of the plurality of nanoparticles, varying a shape of the plurality of nanoparticles, changing a material of the plurality of nanoparticles, adjusting a thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, varying a thickness of the enhancement layer, and/or varying the material of the enhancement layer. The plurality of nanoparticles of the device may be formed from at least one of metal, dielectric material, semiconductor materials, an alloy of metal, a mixture of dielectric materials, a stack or layering of one or more materials, and/or a core of one type of material and that is 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. The plurality of nanoparticles may have additional layer disposed over them. 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 type of polarization that is preferentially outcoupled to air. In some embodiments the outcoupling layer also acts as an electrode of the device.
In yet 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 compounds section of the present disclosure.
In some embodiments, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer can comprise a compound comprising a ligand LA of Formula I described herein.
In some embodiments, the consumer product can be one of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, 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.
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having 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, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. 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 emissive and host materials are disclosed in U.S. Pat. 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. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. 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 may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
The simple layered structure illustrated in
Structures and materials not specifically described may also be used, such as OLEDs comprised of 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 further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons are a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present disclosure may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic 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. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25° C.), but could be used outside this temperature range, for example, from −40 degree C. to +80° C.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.
In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. application Ser. No. 15/700,352, which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from others). When there are more than one ligand coordinated to a metal, the ligands can all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, every ligand can be different from each other. This is also true in embodiments where a ligand being coordinated to a metal can be linked with other ligands being coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, where the coordinating ligands are being linked together, all of the ligands can be the same in some embodiments, and at least one of the ligands being linked can be different from the other ligand(s) in some other embodiments.
In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contains an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 100%. The acceptor could be in either 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 arise from any or all of the sensitizer, acceptor, and final emitter.
According to another aspect, a formulation comprising the compound described herein is also disclosed.
The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. 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.
In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, electron blocking material, hole blocking material, and an electron transport material, disclosed herein.
The present disclosure encompasses any chemical structure comprising the novel compound of the present disclosure, or a monovalent or polyvalent variant thereof. In other words, the inventive compound, or a monovalent or polyvalent variant thereof, can be a part of a larger chemical structure. Such chemical structure can be selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule (also known as supermolecule). As used herein, a “monovalent variant of a compound” refers to a moiety that is identical to the compound except that one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a “polyvalent variant of a compound” refers to a moiety that is identical to the compound except that more than one hydrogen has been removed and replaced with a bond or bonds to the rest of the chemical structure. In the instance of a supramolecule, the inventive compound can also be incorporated into the supramolecule complex without covalent bonds.
D. Combination of the Compounds of the Present Disclosure with Other MaterialsThe materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
a) Conductivity Dopants:A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn 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 may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.
A hole injecting/transporting material to be used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
Each of Ar1 to Ar9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the 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, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:
wherein k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.
Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:
wherein Met is a metal, which can have an atomic weight greater than 40; (Y101-Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, (Y101-Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101-Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.
Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.
An electron blocking layer (EBL) may 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 may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or 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 higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
d) Hosts:The light emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:
wherein Met is a metal; (Y103-Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, the metal complexes are:
wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103-Y104) is a carbene ligand.
In one aspect, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the 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, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, the host compound contains at least one of the following groups in the molecule:
wherein R101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20. X101 to X108 are independently selected from C (including CH) or N. Z101 and Z102 are independently selected from NR101, O, or S.
Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, U.S. Pat. No. 9,466,803,
One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599, U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos. 6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469, 6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228, 7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586, 8,871,361, 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.
A hole blocking layer (HBL) may 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 may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or 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 higher triplet energy than one or more of the hosts closest to the HBL interface.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
wherein k is an integer from 1 to 20; L101 is another ligand, k′ is an integer from 1 to 3.
g) ETL:Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the following groups in the molecule:
wherein R101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar1 to Ar3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X101 to X108 is selected from C (including CH) or N.
In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:
wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,
In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.
E. Experimental Data Synthesis of 2-(Benzyloxy)-6-fluorobenzaldehyde (1)A mixture of 2-fluoro-6-hydroxybenzaldehyde (25.0 g, 178 mmol), K2CO3 (74.0 g, 535 mmol) and benzyl bromide (32 mL, 270 mmol) in dry MeCN (500 mL) under nitrogen was stirred for 18 hours at room temperature (RT). The mixture was filtered, rinsed through with EtOAc (2×150 mL) and the filtrate was concentrated in vacuo. Purification by chromatography gave 2-(benzyloxy)-6-fluorobenzaldehyde (1) (28.5 g, 123 mmol, 69% yield, >98% purity) as a colourless liquid, which crystallized on standing.
Synthesis of 2-(2-(Benzyloxy)-6-fluorophenyl)-1H-imidazole (2)Ammonia (28 wt % in H2O) (100 mL, 1.29 mol) was added to a stirred mixture of glyoxal (40 wt % in H2O) (75 mL, 0.65 mol) and 2-(benzyloxy)-6-fluorobenzaldehyde (1) (28.5 g, 123 mmol) in EtOH (350 mL). The reaction mixture was stirred at 50° C. for 19 hours. Further glyoxal (40 wt % in H2O) (12.0 mL, 262 mmol) was added and the mixture was stirred at 50° C. for 3 hours. The mixture was cooled to RT and concentrated in vacuo. The residue was purified in three equal batches by column chromatography to give a dark brown solid. This solid was triturated with TBME (300 mL), filtered, rinsed with MTBE (2×100 mL) and dried in vacuo to give 2-(2-(benzyloxy)-6-fluorophenyl)-1H-imidazole (2) (16.5 g, 60.3 mmol, 49% yield, >98% purity) as a light brown powder.
Synthesis of 3-(Benzyloxy)-2-(1H-imidazol-2-yl)-N-methylaniline (3)A mixture of isopropylmagnesium chloride (2 M in THF, 150 mL, 300 mmol) in diglyme (300 mL) was cooled to 0° C. and methylamine (2 M in THF, 120 mL, 240 mmol) was added over 5 min. The resulting mixture was stirred at 0° C. for 1 hour, then a suspension of 2-(2-(benzyloxy)-6-fluorophenyl)-1H-imidazole (2) (16.5 g, 60.3 mmol) in diglyme (300 mL) was added over 20 min. The resulting mixture was heated to 110° C. and stirred for 22 hours. The mixture was poured into sat. NH4Cl(aq) (600 mL), diluted with EtOAc (200 mL) and sonicated for 2 min. The layers were separated and the aqueous phase was extracted with EtOAc (3×300 mL). The combined organic extracts were washed with brine (400 mL), dried over MgSO4, filtered and concentrated in vacuo. Purification by column chromatography gave 3-(benzyloxy)-2-(1H-imidazol-2-yl)-N-methylaniline (3) (11.4 g, 36.7 mmol, 61% yield, 90% purity) as a pale yellow solid.
Synthesis of 2-(1H-Imidazol-2-yl)-3-(methylamino)phenol (4)A mixture of 3-(benzyloxy)-2-(1H-imidazol-2-yl)-N-methylaniline (3) (11.4 g, 36.7 mmol) and Pd (10% on C, wetted with 50% water, 1.9 g, 0.69 mmol) in EtOH (150 mL) and THF (80 mL) was stirred in a steel bomb under hydrogen (2 bar) at RT for 2 hours. The mixture was filtered (GF/F glass microfibre pad) and concentrated in vacuo. Purification by column chromatography gave 2-(1H-imidazol-2-yl)-3-(methylamino)phenol (4) (5.46 g, 28.3 mmol, 77% yield, >98% purity) as a brown solid.
Synthesis of 5-(2,6-Diisopropylphenyl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2]diazaborinin-10-ol (5)TMSCl (4.30 mL, 33.6 mmol) was added to solution of potassium (2,6-diisopropylphenyl)trifluoroborate (9.00 g, 33.6 mmol) in dry THF (30 mL) under nitrogen. The resulting mixture was stirred at RT for 1 hour [Solution A].
In a separate flask, n-BuLi (2.5 M in hexanes, 20 mL, 50 mmol) was added a solution of 2-(1H-imidazol-2-yl)-3-(methylamino)phenol (4) (3.00 g, 15.9 mmol) in dry THF (30 mL) under nitrogen at −78° C. The resulting mixture was stirred at −78° C. for 1 hour [Solution B].
Solution A was added to Solution B at −78° C. over 10 min. The mixture was warmed to RT, then stirred at 60° C. for 1 hour. The mixture was cooled to RT, quenched with sat. NH4Cl(aq) (60 mL) and diluted with water(60 mL). The aqueous layer was extracted with EtOAc (120 mL, 3×60 mL) and the combined organic extracts were washed with brine (120 mL), dried over MgSO4, filtered and concentrated in vacuo. Purification by column chromatography gave the product as a white powder (4.6 g, <98% purity). This material was triturated with TBME (20 mL) and the solid was collected by filtration, rinsed with TBME (2×5 mL) and dried in vacuo to give 5-(2,6-diisopropylphenyl)-6-methyl-5,6-dihydrobenzo[e]imidazo[1,2-c][1,3,2] diazaborinin-10-ol (5) (2.63 g, 7.31 mmol, 46% yield, 99.6% HPLC) as a white powder.
Synthesis of Phosphorescent ComplexesA heterogeneous mixture of [IrL2Cl]2 (1 equiv., 0.02 M), (5) (2.2 equiv.), and K2C3 (10 equiv.) in THF was stirred at 60° C. under nitrogen for two days. Solvent was removed in vacuo and the crude residue was purified by column chromatography, yielding the products in 35-65% yields.
Photolumnescent spectra of inventive complexes Ir[LA1-(33)(2)(1)(1)][LB148]2, Ir[LA1-(33)(2)(1)(1)][LB28]2 and Ir[LA1-(33)(2)(1)(1)][LB540]2 are showing in
Device Experimental
Device 1:
OLEDs were grown on a glass substrate pre-coated with an indium-tin-oxide (ITO) layer having a sheet resistance of 15-Ω/sq. Prior to any organic layer deposition or coating, the substrate was degreased with solvents and then treated with an oxygen plasma for 1.5 minutes with 50W at 100 mTorr and with UV ozone for 5 minutes.
The devices in Tables 1 were fabricated in high vacuum (<10-6 Torr) by thermal evaporation. The anode electrode was 750 Å of indium tin oxide (ITO). The device example had organic layers consisting of, sequentially, from the ITO surface, 100 Å of Compound 1 (HIL), 250 Å of Compound 2 (HTL), 50 Å of Compound 3 (EBL), 300 Å of Compound 4 doped with a percentage of Emitter (EML), 50 Å of Compound 5 (BL), 300 Å of Compound 6 (ETL), 10 Å of Compound 7 (EIL) followed by 1,000 Å of A1 (Cathode). All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) immediately after fabrication with a moisture getter incorporated inside the package. Doping percentages are in volume percent.
Device 2:
OLEDs were grown on a glass substrate pre-coated with an indium-tin-oxide (ITO) layer having a sheet resistance of 15-Ω/sq. Prior to any organic layer deposition or coating, the substrate was degreased with solvents and then treated with an oxygen plasma for 1.5 minutes with 50W at 100 mTorr and with UV ozone for 5 minutes.
The devices in Tables 2 were fabricated in high vacuum (<10-6 Torr) by thermal evaporation. The anode electrode was 750 Å of indium tin oxide (ITO). The device example had organic layers consisting of, sequentially, from the ITO surface, 100 Å of Compound 1 (HIL), 400 Å of Compound 2 (HTL), 50 Å of Compound 3 (EBL), 400 Å of Compound 8 doped with Compound 9 (35%) and a percentage of Emitter (EML), 350 Å of Compound 7 doped with Compound 10 (35%) (ETL), 10 Å of Compound 7 (EIL) followed by 1,000 Å of A1 (Cathode). All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) immediately after fabrication with a moisture getter incorporated inside the package. Doping percentages are in volume percent.
The electroluminescent device data for both Ir[LA1-(33)(2)(1)(1)][LB148]2 and Ir[LA1-(33)(2)(1)(1)][LB28]2 also support the benefit of employing the inventive compounds in phosphorescent materials. Not only are the electroluminescent lifetimes maintained when normalized against inventive compounds, but in the case of Ir[LA1-(33)(2)(1)(1)][LB148]2 are improved 2.7-fold. And while the spectral behavior between the inventive and comparative compounds are comparable, there is a reduction in operating voltage as high as 15%, making the inventive ligands effective tools in the design and manufacture of high-efficiency, long-lifetime OLED devices.
Claims
1.-72. (canceled)
73. A compound comprising a ligand LA of Formula I: wherein:
- each of Z1, Z2, Z3, Z4, Z5, and Z6 each independently C or N;
- K is selected from the group consisting of a direct bond, O, and S;
- when K is O or S, then Z6 is C;
- each of ring A1 and ring A2 is independently a 5-membered or 6-membered carbocyclic or heterocyclic rings or a multicyclic fused-ring system comprising more than one 5-membered or 6-membered carbocyclic or heterocyclic ring;
- each of RA and RB is independently mono, up to a maximum allowed substitutions, or no substitution;
- the ligand LA is coordinated to a metal M by the two indicated dash lines;
- M is selected from the group consisting of Ru, Os, Ir, Pd, Pt, Cu, Ag, and Au;
- M is coordinated to at least one other ligand;
- LA can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand;
- L1 is an organic linker,
- when M is selected from the group consisting of Ru, Os, and Ir, then K is O or S;
- when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au, and K is a direct bond, then M forms at least one bond to oxygen or sulfur; and
- when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au, and K is O or S, then LI is selected from the group consisting of —CR═N—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR′NR—, —CR′═CR″CR2—, —C(═N—)—, and —C(═CR—)—;
- each RA, RB, R, R′, R″ is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
- any two adjacent RA, RB, R, R′ and R″ can be joined or fused together to form a ring.
74. The compound of claim 73, wherein each RA, RB, R, R′, R″ is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
75. The compound of claim 73, wherein Z3 is selected from the group consisting of N and carbene carbon; and either Z6 is C and K is O or S; or Z6 is N and K is a direct bond.
76. The compound of claim 73, wherein ring A1 is selected from the group consisting of imidazole, benzimidazole, imidazole-based carbene, benzimidazole-based carbene, pyrimidine, pyrazole, and pyridine; and ring A2 is selected from the group consisting of benzene, pyridine, carbazole, benzimidazole, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, dibenzofluorene, naphthalene, tetrahydronaphthalene, phenoxazine, 9,10-dihydroacridine, anthracene, and phenanthrene.
77. The compound of claim 73, wherein M is selected from the group consisting of Ru, Os, and Ir, and
- K is O or S.
78. The compound of claim 73, wherein the organic linker L1 is selected from the group consisting of —X—, —X—X′—, —XL═XL′—, and —XL═XL′—X—;
- wherein X and X′ are each independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R″, SiR′R″, and GeR′R″; and
- XL and XL′ are each independently selected from the group consisting of N and CR′.
79. The compound of claim 73, wherein M is selected from the group consisting of Pt, Pd, Cu, Ag, or Au, and K is a direct bond; and
- wherein the organic linker L1 is selected from the group consisting of —X—, —X—X′—, —XL═XL′, and —XL═XL′—X—, wherein X and X′ are each independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R″, SiR′R″, and GeR′R″; and
- XL and XL′ are each independently selected from the group consisting of N and CR′.
80. The compound of claim 73, wherein M is selected from the group consisting of Pt, Pd, Cu, Ag, or Au, and K is S or O;
- wherein L1 is selected from the group consisting of —CR═N—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, and —CR′R″S—.
81. The compound of claim 73, wherein the ligand LA is selected from the group consisting of: and wherein each RA, RB, RC, R1, R2, R3, and R4 is independently a 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, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof.
82. The compound of claim 73, wherein the compound has a formula of M(LA)p(LB)q(LC)r wherein LB and LC 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.
83. The compound of claim 82, wherein LB and LC are each independently selected from the group consisting of: wherein:
- T is selected from the group consisting of B, Al, Ga, and In;
- each of Y1 to Y13 is independently selected from the group consisting of carbon and nitrogen;
- Y′ is selected from the group consisting of BRe, NRe, PRe, O, S, Se, C═O, S═O, SO2, CReRf, SiReRf, and GeReRf;
- Re and Rf can be fused or joined to form a ring;
- each Ra, Rb, Rc and Rd independently represents zero, mono, or up to a maximum allowed number of substitutions to its associated ring;
- each of Ra1, Rb1, Rc1, Rd1, Ra, Rb, Rc, Rd, Re and Rf is independently a hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; the general substituents defined herein; and
- any two adjacent Ra, Rb, Rc, Rd, Re and Rf can be fused or joined to form a ring or form a multidentate ligand.
84. The compound of claim 82, wherein when the compound has formula Ir(LA)3, LA is selected from the group consisting of the structures in the following group referred to as LA,spec, wherein each of i, j, k, and l is independently an integer from 1 to 86: LA Structure of LA Definitions LA1-(Ri)(Rj)(Rk)(Rl), where LA1- (R1)(R1)(R1)(R1) to LA1- (R86)(R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, RA3 is Rk, RA4 is Rl, LA2-(Ri)(Rj)(Rk)(Rl), where LA2- (R1)(R1)(R1)(R1) to LA2- (R86)(R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, RA3 is Rk, RA4 is Rl, LA3-(Ri)(Rj)(Rk)(Rl), LA3-(R1)(R1)(R1)(R1) to LA3-(R86)(R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, RA3 is Rk, RA4 is Rl, LA4-(Ri)(Rj)(Rk)(Rl), LA4-(R1)(R1)(R1)(R1) to LA4-(R86)(R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, RA3 is Rk, RA4 is Rl, LA5-(Ri)(Rj)(Rk)(Rl), LA5-(R1)(R1)(R1)(R1) to LA5-(R86)(R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, RA3 is Rk, RA4 is Rl, LA6-(Ri)(Rj)(Rk)(Rl), LA6-(R1)(R1)(R1)(R1) to LA6-(R86)(R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, RA3 is Rk, RA4 is Rl, LA7-(Ri)(Rj), LA7-(R1)(R1) to LA7-(R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA8-(Ri)(Rj), LA8-(R1)(R1) to LA8-(R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA9-(Ri)(Rj), LA9-(R1)(R1) to LA9-(R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA10-(Ri)(Rj), LA10-(R1)(R1) to LA10- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA11-(Ri)(Rj), LA11-(R1)(R1) to LA11- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA12-(Ri)(Rj), LA12-(R1)(R1) to LA12- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA13-(Ri)(Rj), LA13-(R1)(R1) to LA13- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA14-(Ri)(Rj), LA14-(R1)(R1) to LA14- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA15-(Ri)(Rj), LA15-(R1)(R1) to LA15- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA16-(Ri)(Rj), LA16-(R1)(R1) to LA16- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA17-(Ri)(Rj), LA17-(R1)(R1) to LA17- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA18-(Ri)(Rj), LA18-(R1)(R1) to LA18- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA19-(Ri)(Rj), LA19-(R1)(R1) to LA19- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA20-(Ri)(Rj), LA20-(R1)(R1) to LA20- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA21-(Ri)(Rj), LA21-(R1)(R1) to LA21- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA22-(Ri)(Rj), LA22-(R1)(R1) to LA22- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA23-(Ri)(Rj), LA23-(R1)(R1) to LA23- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA24-(Ri)(Rj), LA24-(R1)(R1) to LA24- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA25-(Ri)(Rj), LA25-(R1)(R1) to LA25- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA26-(Ri)(Rj), LA26-(R1)(R1) to LA26- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA27-(Ri)(Rj), LA27-(R1)(R1) to LA27- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA28-(Ri)(Rj), LA28-(R1)(R1) to LA28- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA29-(Ri)(Rj), LA29-(R1)(R1) to LA29- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA30-(Ri)(Rj), LA30-(R1)(R1) to LA30- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA31-(Ri)(Rj), LA31-(R1)(R1) to LA31- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA32-(Ri)(Rj), LA32-(R1)(R1) to LA32- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA33-(Ri)(Rj), LA33-(R1)(R1) to LA33- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA34-(Ri)(Rj), LA34-(R1)(R1) to LA34- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA35-(Ri)(Rj), LA35-(R1)(R1) to LA35- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA36-(Ri)(Rj), LA36-(R1)(R1) to LA36- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA37-(Ri)(Rj), LA37-(R1)(R1) to LA37- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA38-(Ri)(Rj), LA38-(R1)(R1) to LA38- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA39-(Ri)(Rj), LA39-(R1)(R1) to LA39- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA40-(Ri)(Rj), LA40-(R1)(R1) to LA40- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA41-(Ri)(Rj)(Rk), LA41-(R1)(R1)(R1) to LA41- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA42-(Ri)(Rj)(Rk), LA42-(R1)(R1)(R1) to LA42- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA43-(Ri)(Rj), LA43-(R1)(R1) to LA43- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA44-(Ri)(Rj), LA44-(R1)(R1) to LA44- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA45-(Ri)(Rj), LA45-(R1)(R1) to LA45- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA46-(Ri)(Rj), LA46-(R1)(R1) to LA46- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA47-(Ri)(Rj), LA47-(R1)(R1) to LA47- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA48-(Ri)(Rj), LA48-(R1)(R1) to LA48- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA49-(Ri)(Rj), LA49-(R1)(R1) to LA49- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA50-(Ri)(Rj), LA50-(R1)(R1) to LA50- (R86)(R86) have the structure, wherein RA1 is Ri and RA2 is Rj, LA51-(Ri)(Rj)(Rk), LA51-(R1)(R1)(R1) to LA51- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA52-(Ri)(Rj)(Rk), LA52-(R1)(R1)(R1) to LA52- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA53-(Ri)(Rj)(Rk), LA53-(R1)(R1)(R1) to LA53- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA54-(Ri)(Rj)(Rk), LA54-(R1)(R1)(R1) to LA54- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA55-(Ri)(Rj)(Rk), LA55-(R1)(R1)(R1) to LA55- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA56-(Ri)(Rj)(Rk), LA56-(R1)(R1)(R1) to LA56- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA57-(Ri)(Rj)(Rk), LA57-(R1)(R1)(R1) to LA57- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA58-(Ri)(Rj)(Rk), LA58-(R1)(R1)(R1) to LA58- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA59-(Ri)(Rj)(Rk), LA59-(R1)(R1)(R1) to LA59- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA60-(Ri)(Rj)(Rk), LA60-(R1)(R1)(R1) to LA60- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA61-(Ri)(Rj)(Rk), LA61-(R1)(R1)(R1) to LA61- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA62-(Ri)(Rj)(Rk), LA62-(R1)(R1)(R1) to LA62- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA63-(Ri)(Rj)(Rk), LA63-(R1)(R1)(R1) to LA63- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA64-(Ri)(Rj)(Rk), LA64-(R1)(R1)(R1) to LA64- (R86)(R86)(R86) have the structure, wherein RA1 is Ri, RA2 is Rj, and RA3 is Rk, LA65-(Ri), LA65-(R1) to LA65-(R86) have the structure, wherein RA1 is Ri, LA66-(Ri), LA66-(R1) to LA66-(R86) have the structure, wherein RA1 is Ri, LA67-(Ri), LA67-(R1) to LA67-(R86) have the structure, wherein RA1 is Ri, LA68-(Ri), LA68-(R1) to LA68-(R86) have the structure, wherein RA1 is Ri, LA69-(Ri), where LA69-(R1) to LA69-(R86) have the structure, wherein RA1 is Ri, LA70-(Ri), where LA70-(R1) to LA70-(R86) have the structure, wherein RA1 is Ri, LA71-(Ri), where LA71-(R1) to LA71-(R86) have the structure, wherein RA1 is Ri, and the compound is selected from the group consisting of Ir(LA1-(R1)(R1)(R1)(R1))3 to Ir(LA71-(R86))3; and wherein for each LCj in LCj-I and LCj-II, R201 and R202 are each independently defined as follows: LCj R201 R202 LC1 RD1 RD1 LC2 RD2 RD2 LC3 RD3 RD3 LC4 RD4 RD4 LC5 RD5 RD5 LC6 RD6 RD6 LC7 RD7 RD7 LC8 RD8 RD8 LC9 RD9 RD9 LC10 RD10 RD10 LC11 RD11 RD11 LC12 RD12 RD12 LC13 RD13 RD13 LC14 RD14 RD14 LC15 RD15 RD15 LC16 RD16 RD16 LC17 RD17 RD17 LC18 RD18 RD18 LC19 RD19 RD19 LC20 RD20 RD20 LC21 RD21 RD21 LC22 RD22 RD22 LC23 RD23 RD23 LC24 RD24 RD24 LC25 RD25 RD25 LC26 RD26 RD26 LC27 RD27 RD27 LC28 RD28 RD28 LC29 RD29 RD29 LC30 RD30 RD30 LC31 RD31 RD31 LC32 RD32 RD32 LC33 RD33 RD33 LC34 RD34 RD34 LC35 RD35 RD35 LC36 RD36 RD36 LC37 RD37 RD37 LC38 RD38 RD38 LC39 RD39 RD39 LC40 RD40 RD40 LC41 RD41 RD41 LC42 RD42 RD42 LC43 RD43 RD43 LC44 RD44 RD44 LC45 RD45 RD45 LC46 RD46 RD46 LC47 RD47 RD47 LC48 RD48 RD48 LC49 RD49 RD49 LC50 RD50 RD50 LC51 RD51 RD51 LC52 RD52 RD52 LC53 RD53 RD53 LC54 RD54 RD54 LC55 RD55 RD55 LC56 RD56 RD56 LC57 RD57 RD57 LC58 RD58 RD58 LC59 RD59 RD59 LC60 RD60 RD60 LC61 RD61 RD61 LC62 RD62 RD62 LC63 RD63 RD63 LC64 RD64 RD64 LC65 RD65 RD65 LC66 RD66 RD66 LC67 RD67 RD67 LC68 RD68 RD68 LC69 RD69 RD69 LC70 RD70 RD70 LC71 RD71 RD71 LC72 RD72 RD72 LC73 RD73 RD73 LC74 RD74 RD74 LC75 RD75 RD75 LC76 RD76 RD76 LC77 RD77 RD77 LC78 RD78 RD78 LC79 RD79 RD79 LC80 RD80 RD80 LC81 RD81 RD81 LC82 RD82 RD82 LC83 RD83 RD83 LC84 RD84 RD84 LC85 RD85 RD85 LC86 RD86 RD86 LC87 RD87 RD87 LC88 RD88 RD88 LC89 RD89 RD89 LC90 RD90 RD90 LC91 RD91 RD91 LC92 RD92 RD92 LC93 RD93 RD93 LC94 RD94 RD94 LC95 RD95 RD95 LC96 RD96 RD96 LC97 RD97 RD97 LC98 RD98 RD98 LC99 RD99 RD99 LC100 RD100 RD100 LC101 RD101 RD101 LC102 RD102 RD102 LC103 RD103 RD103 LC104 RD104 RD104 LC105 RD105 RD105 LC106 RD106 RD106 LC107 RD107 RD107 LC108 RD108 RD108 LC109 RD109 RD109 LC110 RD110 RD110 LC111 RD111 RD111 LC112 RD112 RD112 LC113 RD113 RD113 LC114 RD114 RD114 LC115 RD115 RD115 LC116 RD116 RD116 LC117 RD117 RD117 LC118 RD118 RD118 LC119 RD119 RD119 LC120 RD120 RD120 LC121 RD121 RD121 LC122 RD122 RD122 LC123 RD123 RD123 LC124 RD124 RD124 LC125 RD125 RD125 LC126 RD126 RD126 LC127 RD127 RD127 LC128 RD128 RD128 LC129 RD129 RD129 LC130 RD130 RD130 LC131 RD131 RD131 LC132 RD132 RD132 LC133 RD133 RD133 LC134 RD134 RD134 LC135 RD135 RD135 LC136 RD136 RD136 LC137 RD137 RD137 LC138 RD138 RD138 LC139 RD139 RD139 LC140 RD140 RD140 LC141 RD141 RD141 LC142 RD142 RD142 LC143 RD143 RD143 LC144 RD144 RD144 LC145 RD145 RD145 LC146 RD146 RD146 LC147 RD147 RD147 LC148 RD148 RD148 LC149 RD149 RD149 LC150 RD150 RD150 LC151 RD151 RD151 LC152 RD152 RD152 LC153 RD153 RD153 LC154 RD154 RD154 LC155 RD155 RD155 LC156 RD156 RD156 LC157 RD157 RD157 LC158 RD158 RD158 LC159 RD159 RD159 LC160 RD160 RD160 LC161 RD161 RD161 LC162 RD162 RD162 LC163 RD163 RD163 LC164 RD164 RD164 LC165 RD165 RD165 LC166 RD166 RD166 LC167 RD167 RD167 LC168 RD168 RD168 LC169 RD169 RD169 LC170 RD170 RD170 LC171 RD171 RD171 LC172 RD172 RD172 LC173 RD173 RD173 LC174 RD174 RD174 LC175 RD175 RD175 LC176 RD176 RD176 LC177 RD177 RD177 LC178 RD178 RD178 LC179 RD179 RD179 LC180 RD180 RD180 LC181 RD181 RD181 LC182 RD182 RD182 LC183 RD183 RD183 LC184 RD184 RD184 LC185 RD185 RD185 LC186 RD186 RD186 LC187 RD187 RD187 LC188 RD188 RD188 LC189 RD189 RD189 LC190 RD190 RD190 LC191 RD191 RD191 LC192 RD192 RD192 LC193 RD1 RD3 LC194 RD1 RD4 LC195 RD1 RD5 LC196 RD1 RD9 LC197 RD1 RD10 LC198 RD1 RD17 LC199 RD1 RD18 LC200 RD1 RD20 LC201 RD1 RD22 LC202 RD1 RD37 LC203 RD1 RD40 LC204 RD1 RD41 LC205 RD1 RD42 LC206 RD1 RD43 LC207 RD1 RD48 LC208 RD1 RD49 LC209 RD1 RD50 LC210 RD1 RD54 LC211 RD1 RD55 LC212 RD1 RD58 LC213 RD1 RD59 LC214 RD1 RD78 LC215 RD1 RD79 LC216 RD1 RD81 LC217 RD1 RD87 LC218 RD1 RD88 LC219 RD1 RD89 LC220 RD1 RD93 LC221 RD1 RD116 LC222 RD1 RD117 LC223 RD1 RD118 LC224 RD1 RD119 LC225 RD1 RD120 LC226 RD1 RD133 LC227 RD1 RD134 LC228 RD1 RD135 LC229 RD1 RD136 LC230 RD1 RD143 LC231 RD1 RD144 LC232 RD1 RD145 LC233 RD1 RD146 LC234 RD1 RD147 LC235 RD1 RD149 LC236 RD1 RD151 LC237 RD1 RD154 LC238 RD1 RD155 LC239 RD1 RD161 LC240 RD1 RD175 LC241 RD4 RD3 LC242 RD4 RD5 LC243 RD4 RD9 LC244 RD4 RD10 LC245 RD4 RD17 LC246 RD4 RD18 LC247 RD4 RD20 LC248 RD4 RD22 LC249 RD4 RD37 LC250 RD4 RD40 LC251 RD4 RD41 LC252 RD4 RD42 LC253 RD4 RD43 LC254 RD4 RD48 LC255 RD4 RD49 LC256 RD4 RD50 LC257 RD4 RD54 LC258 RD4 RD55 LC259 RD4 RD58 LC260 RD4 RD59 LC261 RD4 RD78 LC262 RD4 RD79 LC263 RD4 RD81 LC264 RD4 RD87 LC265 RD4 RD88 LC266 RD4 RD89 LC267 RD4 RD93 LC268 RD4 RD116 LC269 RD4 RD117 LC270 RD4 RD118 LC271 RD4 RD119 LC272 RD4 RD120 LC273 RD4 RD133 LC274 RD4 RD134 LC275 RD4 RD135 LC276 RD4 RD136 LC277 RD4 RD143 LC278 RD4 RD144 LC279 RD4 RD145 LC280 RD4 RD146 LC281 RD4 RD147 LC282 RD4 RD149 LC283 RD4 RD151 LC284 RD4 RD154 LC285 RD4 RD155 LC286 RD4 RD161 LC287 RD4 RD175 LC288 RD9 RD3 LC289 RD9 RD5 LC290 RD9 RD10 LC291 RD9 RD17 LC292 RD9 RD18 LC293 RD9 RD20 LC294 RD9 RD22 LC295 RD9 RD37 LC296 RD9 RD40 LC297 RD9 RD41 LC298 RD9 RD42 LC299 RD9 RD43 LC300 RD9 RD48 LC301 RD9 RD49 LC302 RD9 RD50 LC303 RD9 RD54 LC304 RD9 RD55 LC305 RD9 RD58 LC306 RD9 RD59 LC307 RD9 RD78 LC308 RD9 RD79 LC309 RD9 RD81 LC310 RD9 RD87 LC311 RD9 RD88 LC312 RD9 RD89 LC313 RD9 RD93 LC314 RD9 RD116 LC315 RD9 RD117 LC316 RD9 RD118 LC317 RD9 RD119 LC318 RD9 RD120 LC319 RD9 RD133 LC320 RD9 RD134 LC321 RD9 RD135 LC322 RD9 RD136 LC323 RD9 RD143 LC324 RD9 RD144 LC325 RD9 RD145 LC326 RD9 RD146 LC327 RD9 RD147 LC328 RD9 RD149 LC329 RD9 RD151 LC330 RD9 RD154 LC331 RD9 RD155 LC332 RD9 RD161 LC333 RD9 RD175 LC334 RD10 RD3 LC335 RD10 RD5 LC336 RD10 RD17 LC337 RD10 RD18 LC338 RD10 RD20 LC339 RD10 RD22 LC340 RD10 RD37 LC341 RD10 RD40 LC342 RD10 RD41 LC343 RD10 RD42 LC344 RD10 RD43 LC345 RD10 RD48 LC346 RD10 RD49 LC347 RD10 RD50 LC348 RD10 RD54 LC349 RD10 RD55 LC350 RD10 RD58 LC351 RD10 RD59 LC352 RD10 RD78 LC353 RD10 RD79 LC354 RD10 RD81 LC355 RD10 RD87 LC356 RD10 RD88 LC357 RD10 RD89 LC358 RD10 RD93 LC359 RD10 RD116 LC360 RD10 RD117 LC361 RD10 RD118 LC362 RD10 RD119 LC363 RD10 RD120 LC364 RD10 RD133 LC365 RD10 RD14 LC366 RD10 RD135 LC367 RD10 RD136 LC368 RD10 RD143 LC369 RD10 RD144 LC370 RD10 RD145 LC371 RD10 RD146 LC372 RD10 RD147 LC373 RD10 RD149 LC374 RD10 RD151 LC375 RD10 RD154 LC376 RD10 RD155 LC377 RD10 RD161 LC378 RD10 RD175 LC379 RD17 RD3 LC380 RD17 RD5 LC381 RD17 RD18 LC382 RD17 RD20 LC383 RD17 RD22 LC384 RD17 RD37 LC385 RD17 RD40 LC386 RD17 RD41 LC387 RD17 RD42 LC388 RD17 RD43 LC389 RD17 RD48 LC390 RD17 RD49 LC391 RD17 RD50 LC392 RD17 RD54 LC393 RD17 RD55 LC394 RD17 RD58 LC395 RD17 RD59 LC396 RD17 RD78 LC397 RD17 RD79 LC398 RD17 RD81 LC399 RD17 RD87 LC400 RD17 RD88 LC401 RD17 RD89 LC402 RD17 RD93 LC403 RD17 RD116 LC404 RD17 RD117 LC405 RD17 RD118 LC406 RD17 RD119 LC407 RD17 RD120 LC408 RD17 RD133 LC409 RD17 RD134 LC410 RD17 RD135 LC411 RD17 RD136 LC412 RD17 RD143 LC413 RD17 RD144 LC414 RD17 RD145 LC415 RD17 RD146 LC416 RD17 RD147 LC417 RD17 RD149 LC418 RD17 RD151 LC419 RD17 RD154 LC420 RD17 RD155 LC421 RD17 RD161 LC422 RD17 RD175 LC423 RD50 RD3 LC424 RD50 RD5 LC425 RD50 RD18 LC426 RD50 RD20 LC427 RD50 RD22 LC428 RD50 RD37 LC429 RD50 RD40 LC430 RD50 RD41 LC431 RD50 RD42 LC432 RD50 RD43 LC433 RD50 RD48 LC434 RD50 RD49 LC435 RD50 RD54 LC436 RD50 RD55 LC437 RD50 RD58 LC438 RD50 RD59 LC439 RD50 RD78 LC440 RD50 RD79 LC441 RD50 RD81 LC442 RD50 RD87 LC443 RD50 RD88 LC444 RD50 RD89 LC445 RD50 RD93 LC446 RD50 RD116 LC447 RD50 RD117 LC448 RD50 RD118 LC449 RD50 RD119 LC450 RD50 RD120 LC451 RD50 RD133 LC452 RD50 RD134 LC453 RD50 RD135 LC454 RD50 RD136 LC455 RD50 RD143 LC456 RD50 RD144 LC457 RD50 RD145 LC458 RD50 RD146 LC459 RD50 RD147 LC460 RD50 RD149 LC461 RD50 RD151 LC462 RD50 RD154 LC463 RD50 RD155 LC464 RD50 RD161 LC465 RD50 RD175 LC466 RD55 RD3 LC467 RD55 RD5 LC468 RD55 RD18 LC469 RD55 RD20 LC470 RD55 RD22 LC471 RD55 RD37 LC472 RD55 RD40 LC473 RD55 RD41 LC474 RD55 RD42 LC475 RD55 RD42 LC476 RD55 RD48 LC477 RD55 RD49 LC478 RD55 RD54 LC479 RD55 RD58 LC480 RD55 RD59 LC481 RD55 RD78 LC482 RD55 RD79 LC483 RD55 RD81 LC484 RD55 RD87 LC485 RD55 RD88 LC486 RD55 RD89 LC487 RD55 RD93 LC488 RD55 RD116 LC489 RD55 RD117 LC490 RD55 RD118 LC491 RD55 RD119 LC492 RD55 RD120 LC493 RD55 RD133 LC494 RD55 RD134 LC495 RD55 RD135 LC496 RD55 RD136 LC497 RD55 RD143 LC498 RD55 RD144 LC499 RD55 RD145 LC500 RD55 RD146 LC501 RD55 RD147 LC502 RD55 RD149 LC503 RD55 RD151 LC504 RD55 RD154 LC505 RD55 RD155 LC506 RD55 RD161 LC507 RD55 RD175 LC508 RD116 RD3 LC509 RD116 RD5 LC510 RD116 RD17 LC511 RD116 RD18 LC512 RD116 RD20 LC513 RD116 RD22 LC514 RD116 RD37 LC515 RD116 RD40 LC516 RD116 RD41 LC517 RD116 RD42 LC518 RD116 RD43 LC519 RD116 RD48 LC520 RD116 RD49 LC521 RD116 RD54 LC522 RD116 RD58 LC523 RD116 RD59 LC524 RD116 RD78 LC525 RD116 RD79 LC526 RD116 RD81 LC527 RD116 RD87 LC528 RD116 RD88 LC529 RD116 RD89 LC530 RD116 RD93 LC531 RD116 RD117 LC532 RD116 RD118 LC533 RD116 RD119 LC534 RD116 RD120 LC535 RD116 RD133 LC536 RD116 RD134 LC537 RD116 RD135 LC538 RD116 RD136 LC539 RD116 RD143 LC540 RD116 RD144 LC541 RD116 RD145 LC542 RD116 RD146 LC543 RD116 RD147 LC544 RD116 RD149 LC545 RD116 RD151 LC546 RD116 RD154 LC547 RD116 RD155 LC548 RD116 RD161 LC549 RD116 RD175 LC550 RD143 RD3 LC551 RD143 RD5 LC552 RD143 RD17 LC553 RD143 RD18 LC554 RD143 RD20 LC555 RD143 RD22 LC556 RD143 RD37 LC557 RD143 RD40 LC558 RD143 RD41 LC559 RD143 RD42 LC560 RD143 RD43 LC561 RD143 RD48 LC562 RD143 RD49 LC563 RD143 RD54 LC564 RD143 RD58 LC565 RD143 RD59 LC566 RD143 RD78 LC567 RD143 RD79 LC568 RD143 RD81 LC569 RD143 RD87 LC570 RD143 RD88 LC571 RD143 RD89 LC572 RD143 RD93 LC573 RD143 RD116 LC574 RD143 RD117 LC575 RD143 RD118 LC576 RD143 RD119 LC577 RD143 RD120 LC578 RD143 RD133 LC579 RD143 RD134 LC580 RD143 RD135 LC581 RD143 RD136 LC582 RD143 RD144 LC583 RD143 RD145 LC584 RD143 RD146 LC585 RD143 RD147 LC586 RD143 RD149 LC587 RD143 RD151 LC588 RD143 RD154 LC589 RD143 RD155 LC590 RD143 RD161 LC591 RD143 RD175 LC592 RD144 RD3 LC593 RD144 RD5 LC594 RD144 RD17 LC595 RD144 RD18 LC596 RD144 RD20 LC597 RD144 RD22 LC598 RD144 RD37 LC599 RD144 RD40 LC600 RD144 RD41 LC601 RD144 RD42 LC602 RD144 RD43 LC603 RD144 RD48 LC604 RD144 RD49 LC605 RD144 RD54 LC606 RD144 RD58 LC607 RD144 RD59 LC608 RD144 RD78 LC609 RD144 RD79 LC610 RD144 RD81 LC611 RD144 RD87 LC612 RD144 RD88 LC613 RD144 RD89 LC614 RD144 RD93 LC615 RD144 RD116 LC616 RD144 RD117 LC617 RD144 RD118 LC618 RD144 RD119 LC619 RD144 RD120 LC620 RD144 RD133 LC621 RD144 RD134 LC622 RD144 RD135 LC623 RD144 RD136 LC624 RD144 RD145 LC625 RD144 RD146 LC626 RD144 RD147 LC627 RD144 RD149 LC628 RD144 RD151 LC629 RD144 RD154 LC630 RD144 RD155 LC631 RD144 RD161 LC632 RD144 RD175 LC633 RD145 RD3 LC634 RD145 RD5 LC635 RD145 RD17 LC636 RD145 RD18 LC637 RD145 RD20 LC638 RD145 RD22 LC639 RD145 RD37 LC640 RD145 RD40 LC641 RD145 RD41 LC642 RD145 RD42 LC643 RD145 RD43 LC644 RD145 RD48 LC645 RD145 RD49 LC646 RD145 RD54 LC647 RD145 RD58 LC648 RD145 RD59 LC649 RD145 RD78 LC650 RD145 RD79 LC651 RD145 RD81 LC652 RD145 RD87 LC653 RD145 RD88 LC654 RD145 RD89 LC655 RD145 RD93 LC656 RD145 RD116 LC657 RD145 RD117 LC658 RD145 RD118 LC659 RD145 RD119 LC660 RD145 RD120 LC661 RD145 RD133 LC662 RD145 RD134 LC663 RD145 RD135 LC664 RD145 RD136 LC665 RD145 RD146 LC666 RD145 RD147 LC667 RD145 RD149 LC668 RD145 RD151 LC669 RD145 RD154 LC670 RD145 RD155 LC671 RD145 RD161 LC672 RD145 RD175 LC673 RD146 RD3 LC674 RD146 RD5 LC675 RD146 RD17 LC676 RD146 RD18 LC677 RD146 RD20 LC678 RD146 RD22 LC679 RD146 RD37 LC680 RD146 RD40 LC681 RD146 RD41 LC682 RD146 RD42 LC683 RD146 RD43 LC684 RD146 RD48 LC685 RD146 RD49 LC686 RD146 RD54 LC687 RD146 RD58 LC688 RD146 RD59 LC689 RD146 RD78 LC690 RD146 RD79 LC691 RD146 RD81 LC692 RD146 RD87 LC693 RD146 RD88 LC694 RD146 RD89 LC695 RD146 RD93 LC696 RD146 RD117 LC697 RD146 RD118 LC698 RD146 RD119 LC699 RD146 RD120 LC700 RD146 RD133 LC701 RD146 RD134 LC702 RD146 RD135 LC703 RD146 RD136 LC704 RD146 RD146 LC705 RD146 RD147 LC706 RD146 RD149 LC707 RD146 RD151 LC708 RD146 RD154 LC709 RD146 RD155 LC710 RD146 RD161 LC711 RD146 RD175 LC712 RD133 RD3 LC713 RD133 RD5 LC714 RD133 RD3 LC715 RD133 RD18 LC716 RD133 RD20 LC717 RD133 RD22 LC718 RD133 RD37 LC719 RD133 RD40 LC720 RD133 RD41 LC721 RD133 RD42 LC722 RD133 RD43 LC723 RD133 RD48 LC724 RD133 RD49 LC725 RD133 RD54 LC726 RD133 RD58 LC727 RD133 RD59 LC728 RD133 RD78 LC729 RD133 RD79 LC730 RD133 RD81 LC731 RD133 RD87 LC732 RD133 RD88 LC733 RD133 RD89 LC734 RD133 RD93 LC735 RD133 RD117 LC736 RD133 RD118 LC737 RD133 RD119 LC738 RD133 RD120 LC739 RD133 RD133 LC740 RD133 RD134 LC741 RD133 RD135 LC742 RD133 RD136 LC743 RD133 RD146 LC744 RD133 RD147 LC745 RD133 RD149 LC746 RD133 RD151 LC747 RD133 RD154 LC748 RD133 RD155 LC749 RD133 RD161 LC750 RD133 RD175 LC751 RD175 RD3 LC752 RD175 RD5 LC753 RD175 RD18 LC754 RD175 RD20 LC755 RD175 RD22 LC756 RD175 RD37 LC757 RD175 RD40 LC758 RD175 RD41 LC759 RD175 RD42 LC760 RD175 RD43 LC761 RD175 RD48 LC762 RD175 RD49 LC763 RD175 RD54 LC764 RD175 RD58 LC765 RD175 RD59 LC766 RD175 RD78 LC767 RD175 RD79 LC768 RD175 RD81 LC769 RD193 RD193 LC770 RD194 RD194 LC771 RD195 RD195 LC772 RD196 RD196 LC773 RD197 RD197 LC774 RD198 RD198 LC775 RD199 RD199 LC776 RD200 RD200 LC777 RD201 RD201 LC778 RD202 RD202 LC779 RD203 RD203 LC780 RD204 RD204 LC781 RD205 RD205 LC782 RD206 RD206 LC783 RD207 RD207 LC784 RD208 RD208 LC785 RD209 RD209 LC786 RD210 RD210 LC787 RD211 RD211 LC788 RD212 RD212 LC789 RD213 RD213 LC790 RD214 RD214 LC791 RD215 RD215 LC792 RD216 RD216 LC793 RD217 RD217 LC794 RD218 RD218 LC795 RD219 RD219 LC796 RD220 RD220 LC797 RD221 RD221 LC798 RD222 RD222 LC799 RD223 RD223 LC800 RD224 RD224 LC801 RD225 RD225 LC802 RD226 RD226 LC803 RD227 RD227 LC804 RD228 RD228 LC805 RD229 RD229 LC806 RD230 RD230 LC807 RD231 RD231 LC808 RD232 RD232 LC809 RD233 RD233 LC810 RD234 RD234 LC811 RD235 RD235 LC812 RD236 RD236 LC813 RD237 RD237 LC814 RD238 RD238 LC815 RD239 RD239 LC816 RD240 RD240 LC817 RD241 RD241 LC818 RD242 RD242 LC819 RD243 RD243 LC820 RD244 RD244 LC821 RD245 RD245 LC822 RD246 RD246 LC823 RD17 RD193 LC824 RD17 RD194 LC825 RD17 RD195 LC826 RD17 RD196 LC827 RD17 RD197 LC828 RD17 RD198 LC829 RD17 RD199 LC830 RD17 RD200 LC831 RD17 RD201 LC832 RD17 RD202 LC833 RD17 RD203 LC834 RD17 RD204 LC835 RD17 RD205 LC836 RD17 RD206 LC837 RD17 RD207 LC838 RD17 RD208 LC839 RD17 RD209 LC840 RD17 RD210 LC841 RD17 RD211 LC842 RD17 RD212 LC843 RD17 RD213 LC844 RD17 RD214 LC845 RD17 RD215 LC846 RD17 RD216 LC847 RD17 RD217 LC848 RD17 RD218 LC849 RD17 RD219 LC850 RD17 RD220 LC851 RD17 RD221 LC852 RD17 RD222 LC853 RD17 RD223 LC854 RD17 RD224 LC855 RD17 RD225 LC856 RD17 RD226 LC857 RD17 RD227 LC858 RD17 RD228 LC859 RD17 RD229 LC860 RD17 RD230 LC861 RD17 RD231 LC862 RD17 RD232 LC863 RD17 RD233 LC864 RD17 RD234 LC865 RD17 RD235 LC866 RD17 RD236 LC867 RD17 RD237 LC868 RD17 RD238 LC869 RD17 RD239 LC870 RD17 RD240 LC871 RD17 RD241 LC872 RD17 RD242 LC873 RD17 RD243 LC874 RD17 RD244 LC875 RD17 RD245 LC876 RD17 RD246 LC877 RD1 RD193 LC878 RD1 RD194 LC879 RD1 RD195 LC880 RD1 RD196 LC881 RD1 RD197 LC882 RD1 RD198 LC883 RD1 RD199 LC884 RD1 RD200 LC885 RD1 RD201 LC886 RD1 RD202 LC887 RD1 RD203 LC888 RD1 RD204 LC889 RD1 RD205 LC890 RD1 RD206 LC891 RD1 RD207 LC892 RD1 RD208 LC893 RD1 RD209 LC894 RD1 RD210 LC895 RD1 RD211 LC896 RD1 RD212 LC897 RD1 RD213 LC898 RD1 RD214 LC899 RD1 RD215 LC900 RD1 RD216 LC901 RD1 RD217 LC902 RD1 RD218 LC903 RD1 RD219 LC904 RD1 RD220 LC905 RD1 RD221 LC906 RD1 RD222 LC907 RD1 RD223 LC908 RD1 RD224 LC909 RD1 RD225 LC910 RD1 RD226 LC911 RD1 RD227 LC912 RD1 RD228 LC913 RD1 RD229 LC914 RD1 RD230 LC915 RD1 RD231 LC916 RD1 RD232 LC917 RD1 RD233 LC918 RD1 RD234 LC919 RD1 RD235 LC920 RD1 RD236 LC921 RD1 RD237 LC922 RD1 RD238 LC923 RD1 RD239 LC924 RD1 RD240 LC925 RD1 RD241 LC926 RD1 RD242 LC927 RD1 RD243 LC928 RD1 RD244 LC929 RD1 RD245 LC930 RD1 RD246 LC931 RD50 RD193 LC932 RD50 RD194 LC933 RD50 RD195 LC934 RD50 RD196 LC935 RD50 RD197 LC936 RD50 RD198 LC937 RD50 RD199 LC938 RD50 RD200 LC939 RD50 RD201 LC940 RD50 RD202 LC941 RD50 RD203 LC942 RD50 RD204 LC943 RD50 RD205 LC944 RD50 RD206 LC945 RD50 RD207 LC946 RD50 RD208 LC947 RD50 RD209 LC948 RD50 RD210 LC949 RD50 RD211 LC950 RD50 RD212 LC951 RD50 RD213 LC952 RD50 RD214 LC953 RD50 RD215 LC954 RD50 RD216 LC955 RD50 RD217 LC956 RD50 RD218 LC957 RD50 RD219 LC958 RD50 RD220 LC959 RD50 RD221 LC960 RD50 RD222 LC961 RD50 RD223 LC962 RD50 RD224 LC963 RD50 RD225 LC964 RD50 RD226 LC965 RD50 RD227 LC966 RD50 RD228 LC967 RD50 RD229 LC968 RD50 RD230 LC969 RD50 RD231 LC970 RD50 RD232 LC971 RD50 RD233 LC972 RD50 RD234 LC973 RD50 RD235 LC974 RD50 RD236 LC975 RD50 RD237 LC976 RD50 RD238 LC977 RD50 RD239 LC978 RD50 RD240 LC979 RD50 RD241 LC980 RD50 RD242 LC981 RD50 RD243 LC982 RD50 RD244 LC983 RD50 RD245 LC984 RD50 RD246 LC985 RD4 RD193 LC986 RD4 RD194 LC987 RD4 RD195 LC988 RD4 RD196 LC989 RD4 RD197 LC990 RD4 RD198 LC991 RD4 RD199 LC992 RD4 RD200 LC993 RD4 RD201 LC994 RD4 RD202 LC995 RD4 RD203 LC996 RD4 RD204 LC997 RD4 RD205 LC998 RD4 RD206 LC999 RD4 RD207 LC1000 RD4 RD208 LC1001 RD4 RD209 LC1002 RD4 RD210 LC1003 RD4 RD211 LC1004 RD4 RD212 LC1005 RD4 RD213 LC1006 RD4 RD214 LC1007 RD4 RD215 LC1008 RD4 RD216 LC1009 RD4 RD217 LC1010 RD4 RD218 LC1011 RD4 RD219 LC1012 RD4 RD220 LC1013 RD4 RD221 LC1014 RD4 RD222 LC1015 RD4 RD223 LC1016 RD4 RD224 LC1017 RD4 RD225 LC1018 RD4 RD226 LC1019 RD4 RD227 LC1020 RD4 RD228 LC1021 RD4 RD229 LC1022 RD4 RD230 LC1023 RD4 RD231 LC1024 RD4 RD232 LC1025 RD4 RD233 LC1026 RD4 RD234 LC1027 RD4 RD235 LC1028 RD4 RD236 LC1029 RD4 RD237 LC1030 RD4 RD238 LC1031 RD4 RD239 LC1032 RD4 RD240 LC1033 RD4 RD241 LC1034 RD4 RD242 LC1035 RD4 RD243 LC1036 RD4 RD244 LC1037 RD4 RD245 LC1038 RD4 RD246 LC1039 RD145 RD193 LC1040 RD145 RD194 LC1041 RD145 RD195 LC1042 RD145 RD196 LC1043 RD145 RD197 LC1044 RD145 RD198 LC1045 RD145 RD199 LC1046 RD145 RD200 LC1047 RD145 RD201 LC1048 RD145 RD202 LC1049 RD145 RD203 LC1050 RD145 RD204 LC1051 RD145 RD205 LC1052 RD145 RD206 LC1053 RD145 RD207 LC1054 RD145 RD208 LC1055 RD145 RD209 LC1056 RD145 RD210 LC1057 RD145 RD211 LC1058 RD145 RD212 LC1059 RD145 RD213 LC1060 RD145 RD214 LC1061 RD145 RD215 LC1062 RD145 RD216 LC1063 RD145 RD217 LC1064 RD145 RD218 LC1065 RD145 RD219 LC1066 RD145 RD220 LC1067 RD145 RD221 LC1068 RD145 RD222 LC1069 RD145 RD223 LC1070 RD145 RD224 LC1071 RD145 RD225 LC1072 RD145 RD226 LC1073 RD145 RD227 LC1074 RD145 RD228 LC1075 RD145 RD229 LC1076 RD145 RD230 LC1077 RD145 RD231 LC1078 RD145 RD232 LC1079 RD145 RD233 LC1080 RD145 RD234 LC1081 RD145 RD235 LC1082 RD145 RD236 LC1083 RD145 RD237 LC1084 RD145 RD238 LC1085 RD145 RD239 LC1086 RD145 RD240 LC1087 RD145 RD241 LC1088 RD145 RD242 LC1089 RD145 RD243 LC1090 RD145 RD244 LC1091 RD145 RD245 LC1092 RD145 RD246 LC1093 RD9 RD193 LC1094 RD9 RD194 LC1095 RD9 RD195 LC1096 RD9 RD196 LC1097 RD9 RD197 LC1098 RD9 RD198 LC1099 RD9 RD199 LC1100 RD9 RD200 LC1101 RD9 RD201 LC1102 RD9 RD202 LC1103 RD9 RD203 LC1104 RD9 RD204 LC1105 RD9 RD205 LC1106 RD9 RD206 LC1107 RD9 RD207 LC1108 RD9 RD208 LC1109 RD9 RD209 LC1110 RD9 RD210 LC1111 RD9 RD211 LC1112 RD9 RD212 LC1113 RD9 RD213 LC1114 RD9 RD214 LC1115 RD9 RD215 LC1116 RD9 RD216 LC1117 RD9 RD217 LC1118 RD9 RD218 LC1119 RD9 RD219 LC1120 RD9 RD220 LC1121 RD9 RD221 LC1122 RD9 RD222 LC1123 RD9 RD223 LC1124 RD9 RD224 LC1125 RD9 RD225 LC1126 RD9 RD226 LC1127 RD9 RD227 LC1128 RD9 RD228 LC1129 RD9 RD229 LC1130 RD9 RD230 LC1131 RD9 RD231 LC1132 RD9 RD232 LC1133 RD9 RD233 LC1134 RD9 RD234 LC1135 RD9 RD235 LC1136 RD9 RD236 LC1137 RD9 RD237 LC1138 RD9 RD238 LC1139 RD9 RD239 LC1140 RD9 RD240 LC1141 RD9 RD241 LC1142 RD9 RD242 LC1143 RD9 RD243 LC1144 RD9 RD244 LC1145 RD9 RD245 LC1146 RD9 RD246 LC1147 RD168 RD193 LC1148 RD168 RD194 LC1149 RD168 RD195 LC1150 RD168 RD196 LC1151 RD168 RD197 LC1152 RD168 RD198 LC1153 RD168 RD199 LC1154 RD168 RD200 LC1155 RD168 RD201 LC1156 RD168 RD202 LC1157 RD168 RD203 LC1158 RD168 RD204 LC1159 RD168 RD205 LC1160 RD168 RD206 LC1161 RD168 RD207 LC1162 RD168 RD208 LC1163 RD168 RD209 LC1164 RD168 RD210 LC1165 RD168 RD211 LC1166 RD168 RD212 LC1167 RD168 RD213 LC1168 RD168 RD214 LC1169 RD168 RD215 LC1170 RD168 RD216 LC1171 RD168 RD217 LC1172 RD168 RD218 LC1173 RD168 RD219 LC1174 RD168 RD220 LC1175 RD168 RD221 LC1176 RD168 RD222 LC1177 RD168 RD223 LC1178 RD168 RD224 LC1179 RD168 RD225 LC1180 RD168 RD226 LC1181 RD168 RD227 LC1182 RD168 RD228 LC1183 RD168 RD229 LC1184 RD168 RD230 LC1185 RD168 RD231 LC1186 RD168 RD232 LC1187 RD168 RD233 LC1188 RD168 RD234 LC1189 RD168 RD235 LC1190 RD168 RD236 LC1191 RD168 RD237 LC1192 RD168 RD238 LC1193 RD168 RD239 LC1194 RD168 RD240 LC1195 RD168 RD241 LC1196 RD168 RD242 LC1197 RD168 RD243 LC1198 RD168 RD244 LC1199 RD168 RD245 LC1200 RD168 RD246 LC1201 RD10 RD193 LC1202 RD10 RD194 LC1203 RD10 RD195 LC1204 RD10 RD196 LC1205 RD10 RD197 LC1206 RD10 RD198 LC1207 RD10 RD199 LC1208 RD10 RD200 LC1209 RD10 RD201 LC1210 RD10 RD202 LC1211 RD10 RD203 LC1212 RD10 RD204 LC1213 RD10 RD205 LC1214 RD10 RD206 LC1215 RD10 RD207 LC1216 RD10 RD208 LC1217 RD10 RD209 LC1218 RD10 RD210 LC1219 RD10 RD211 LC1220 RD10 RD212 LC1221 RD10 RD213 LC1222 RD10 RD214 LC1223 RD10 RD215 LC1224 RD10 RD216 LC1225 RD10 RD217 LC1226 RD10 RD218 LC1227 RD10 RD219 LC1228 RD10 RD220 LC1229 RD10 RD221 LC1230 RD10 RD222 LC1231 RD10 RD223 LC1232 RD10 RD224 LC1233 RD10 RD225 LC1234 RD10 RD226 LC1235 RD10 RD227 LC1236 RD10 RD228 LC1237 RD10 RD229 LC1238 RD10 RD230 LC1239 RD10 RD231 LC1240 RD10 RD232 LC1241 RD10 RD233 LC1242 RD10 RD234 LC1243 RD10 RD235 LC1244 RD10 RD236 LC1245 RD10 RD237 LC1246 RD10 RD238 LC1247 RD10 RD239 LC1248 RD10 RD240 LC1249 RD10 RD241 LC1250 RD10 RD242 LC1251 RD10 RD243 LC1252 RD10 RD244 LC1253 RD10 RD245 LC1254 RD10 RD246 LC1255 RD55 RD193 LC1256 RD55 RD194 LC1257 RD55 RD195 LC1258 RD55 RD196 LC1259 RD55 RD197 LC1260 RD55 RD198 LC1261 RD55 RD199 LC1262 RD55 RD200 LC1263 RD55 RD201 LC1264 RD55 RD202 LC1265 RD55 RD203 LC1266 RD55 RD204 LC1267 RD55 RD205 LC1268 RD55 RD206 LC1269 RD55 RD207 LC1270 RD55 RD208 LC1271 RD55 RD209 LC1272 RD55 RD210 LC1273 RD55 RD211 LC1274 RD55 RD212 LC1275 RD55 RD213 LC1276 RD55 RD214 LC1277 RD55 RD215 LC1278 RD55 RD216 LC1279 RD55 RD217 LC1280 RD55 RD218 LC1281 RD55 RD219 LC1282 RD55 RD220 LC1283 RD55 RD221 LC1284 RD55 RD222 LC1285 RD55 RD223 LC1286 RD55 RD224 LC1287 RD55 RD225 LC1288 RD55 RD226 LC1289 RD55 RD227 LC1290 RD55 RD228 LC1291 RD55 RD229 LC1292 RD55 RD230 LC1293 RD55 RD231 LC1294 RD55 RD232 LC1295 RD55 RD233 LC1296 RD55 RD234 LC1297 RD55 RD235 LC1298 RD55 RD236 LC1299 RD55 RD237 LC1300 RD55 RD238 LC1301 RD55 RD239 LC1302 RD55 RD240 LC1303 RD55 RD241 LC1304 RD55 RD242 LC1305 RD55 RD243 LC1306 RD55 RD244 LC1307 RD55 RD245 LC1308 RD55 RD246 LC1309 RD37 RD193 LC1310 RD37 RD194 LC1311 RD37 RD195 LC1312 RD37 RD196 LC1313 RD37 RD197 LC1314 RD37 RD198 LC1315 RD37 RD199 LC1316 RD37 RD200 LC1317 RD37 RD201 LC1318 RD37 RD202 LC1319 RD37 RD203 LC1320 RD37 RD204 LC1321 RD37 RD205 LC1322 RD37 RD206 LC1323 RD37 RD207 LC1324 RD37 RD208 LC1325 RD37 RD209 LC1326 RD37 RD210 LC1327 RD37 RD211 LC1328 RD37 RD212 LC1329 RD37 RD213 LC1330 RD37 RD214 LC1331 RD37 RD215 LC1332 RD37 RD216 LC1333 RD37 RD217 LC1334 RD37 RD218 LC1335 RD37 RD219 LC1336 RD37 RD220 LC1337 RD37 RD221 LC1338 RD37 RD222 LC1339 RD37 RD223 LC1340 RD37 RD224 LC1341 RD37 RD225 LC1342 RD37 RD226 LC1343 RD37 RD227 LC1344 RD37 RD228 LC1345 RD37 RD229 LC1346 RD37 RD230 LC1347 RD37 RD231 LC1348 RD37 RD232 LC1349 RD37 RD233 LC1350 RD37 RD234 LC1351 RD37 RD235 LC1352 RD37 RD236 LC1353 RD37 RD237 LC1354 RD37 RD238 LC1355 RD37 RD239 LC1356 RD37 RD240 LC1357 RD37 RD241 LC1358 RD37 RD242 LC1359 RD37 RD243 LC1360 RD37 RD244 LC1361 RD37 RD245 LC1362 RD37 RD246 LC1363 RD143 RD193 LC1364 RD143 RD194 LC1365 RD143 RD195 LC1366 RD143 RD196 LC1367 RD143 RD197 LC1368 RD143 RD198 LC1369 RD143 RD199 LC1370 RD143 RD200 LC1371 RD143 RD201 LC1372 RD143 RD202 LC1373 RD143 RD203 LC1374 RD143 RD204 LC1375 RD143 RD205 LC1376 RD143 RD206 LC1377 RD143 RD207 LC1378 RD143 RD208 LC1379 RD143 RD209 LC1380 RD143 RD210 LC1381 RD143 RD211 LC1382 RD143 RD212 LC1383 RD143 RD213 LC1384 RD143 RD214 LC1385 RD143 RD215 LC1386 RD143 RD216 LC1387 RD143 RD217 LC1388 RD143 RD218 LC1389 RD143 RD219 LC1390 RD143 RD220 LC1391 RD143 RD221 LC1392 RD143 RD222 LC1393 RD143 RD223 LC1394 RD143 RD224 LC1395 RD143 RD225 LC1396 RD143 RD226 LC1397 RD143 RD227 LC1398 RD143 RD228 LC1399 RD143 RD229 LC1400 RD143 RD230 LC1401 RD143 RD231 LC1402 RD143 RD232 LC1403 RD143 RD233 LC1404 RD143 RD234 LC1405 RD143 RD235 LC1406 RD143 RD236 LC1407 RD143 RD237 LC1408 RD143 RD238 LC1409 RD143 RD239 LC1410 RD143 RD240 LC1411 RD143 RD241 LC1412 RD143 RD242 LC1413 RD143 RD243 LC1414 RD143 RD244 LC1415 RD143 RD245 LC1416 RD143 RD246 wherein RD1 to RD246 have the following structures:
- wherein Ph represents phenyl; and
- wherein R1 to R86 have the following structures:
- when the compound has formula Ir(LA)(LBk)2, LA is selected from the group consisting of the structures of LA,spec; k is an integer from 1 to 540; and the compound is selected from the group consisting of Ir(LA1-(R1)(R1)(R1)(R1))(LB1)2 to Ir(LA71-(R86))(LB540)2;
- when the compound has formula Ir(LAi-m)2(LBk), LA is selected from the group consisting of the structures of LA,spec; k is an integer from 1 to 540; and the compound is selected from the group consisting of Ir(LA1-(R1)(R1)(R1)(R1))2(LB1) to Ir(LA71-(R86))2(LB540);
- when the compound has formula Ir(LAi-m)2(LCj-I), LA is selected from the group consisting of the structures of LA,spec; j is an integer from 1 to 1416; and the compound is selected from the group consisting of Ir(LA1-(R1)(R1)(R1)(R1))2(LCj-I) to Ir(LA71-(R86))(LC1416-I); and
- when the compound has formula Ir(LAi-m)2(LCj-II), LA is selected from the group consisting of the structures of LA,spec; j is an integer from 1 to 1416; and the compound is selected from the group consisting of Ir(LA1-(R1)(R1)(R1)(R1))2(LC1-II) to Ir(LA71-(R86))(LC1416-II);
- wherein LB1 to LB540 have the following structures:
- wherein each LCj-I has a structure based on formula
- each LCj-II has a structure based on formula
85. The compound of claim 82, wherein the compound has the Formula II: wherein:
- M1 is Pd or Pt;
- rings E and F are each independently a 5-membered or 6-membered carbocyclic or heterocyclic ring;
- Z and Z′ are each independently C or N;
- K1 and K2 are each independently selected from the group consisting of a direct bond, O, and S, wherein at least one of K1 and K2 is a direct bond;
- L1 is an organic linker,
- L2, L3 and L4 are each independently selected from the group consisting of a single bond, absent a bond, O, S, CR′R″, SiR′R″, BR′, and NR′, wherein at least one of L2, L3 and L4 is present;
- X3 and X4 are each independently C or N;
- RE and RF each independently represent zero, mono, or up to a maximum allowed substitution to its associated ring;
- each of R′, R″, RE, and RF is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof; and
- any two adjacent RA, RB, R, R′, R″ RE, and RF can be joined or fused together to forma ring.
86. The compound of claim 85, wherein ring E and ring F are both 6-membered aromatic rings; or
- ring F is a 5-membered or 6-membered heteroaromatic ring.
87. The compound of claim 85, wherein L1 is O or CR′R″; and L2 is a direct bond or NR′.
88. The compound of claim 85, wherein the compound is selected from the group consisting of: wherein:
- L1a is selected from the group of —CR═N—, —CR′R″CR′R″—, —NR′BR—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR″NR—, —CR′═CR″CR2—, —C(═CR—)—, and —C(═N—)—;
- L1b is selected from the group of —CR═N—, —CR2—, —CR═CR′—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR″NR—, —CR′═CR″CR2—, —C(═CR—)—, and —C(═N—)—;
- RY are each selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;
- each RG is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof; and
- any two RA, RB, RE, RF, RG, RY, R, R′ and R″ can be joined together to form a ring.
89. An organic light emitting device (OLED) comprising: wherein:
- an anode;
- a cathode; and
- an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound comprising a ligand LA of Formula I:
- each of Z1, Z2, Z3, Z4, Z5, and Z6 each independently C or N;
- K is selected from the group consisting of a direct bond, O, and S;
- when K is O or S, then Z6 is C;
- each of ring A1 and ring A2 is independently a 5-membered or 6-membered carbocyclic or heterocyclic rings or a multicyclic fused-ring system comprising more than one 5-membered or 6-membered carbocyclic or heterocyclic ring;
- each of RA and RB is independently mono, up to a maximum allowed substitutions, or no substitution;
- the ligand LA is coordinated to a metal M by the two indicated dash lines;
- M is selected from the group consisting of Ru, Os, Ir, Pd, Pt, Cu, Ag, and Au;
- M is coordinated to at least one other ligand;
- LA can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand;
- L1 is an organic linker,
- when M is selected from the group consisting of Ru, Os, and Ir, then K is O or S;
- when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au, and K is a direct bond, then M forms at least one bond to oxygen or sulfur, and
- when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au, and K is O or S, then L1 is selected from the group consisting of —CR═N—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR′NR—, —CR′═CR″CR2—, —C(═N—)—, and —C(═CR—)—;
- each RA, RB, R, R′, R″ is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
- any two adjacent RA, RB, R, R′ and R″ can be joined or fused together to form a ring.
90. The OLED of claim 89, wherein the organic layer further comprises a host, wherein host comprises at least one chemical moiety selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).
91. The OLED of claim 90, wherein the host is selected from the group consisting of: and combinations thereof.
92. A consumer product comprising an organic light-emitting device (OLED) comprising: wherein: any two adjacent RA, RB, R, R′ and R″ can be joined or fused together to form a ring.
- an anode;
- a cathode; and
- an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound comprising a ligand LA of Formula I:
- each of Z1, Z2, Z3, Z4, Z5, and Z6 each independently C or N;
- K is selected from the group consisting of a direct bond, O, and S;
- when K is O or S, then Z6 is C;
- each of ring A1 and ring A2 is independently a 5-membered or 6-membered carbocyclic or heterocyclic rings or a multicyclic fused-ring system comprising more than one 5-membered or 6-membered carbocyclic or heterocyclic ring;
- each of RA and RB is independently mono, up to a maximum allowed substitutions, or no substitution;
- the ligand LA is coordinated to a metal M by the two indicated dash lines;
- M is selected from the group consisting of Ru, Os, Ir, Pd, Pt, Cu, Ag, and Au;
- M is coordinated to at least one other ligand;
- LA can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand;
- L1 is an organic linker,
- when M is selected from the group consisting of Ru, Os, and Ir, then K is O or S;
- when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au, and K is a direct bond, then M forms at least one bond to oxygen or sulfur, and
- when M is selected from the group consisting of Pt, Pd, Cu, Ag, and Au, and K is O or S, then LI is selected from the group consisting of —CR═N—, —CR′R″CR′R″—, —NR′BR′—, —CR′R″O—, —CR′R″S—, —CR′═CR″O—, —CR′═CR″S—, —CR′═CR′NR—, —CR′═CR″CR2—, —C(═N—)—, and —C(═CR—)—;
- each RA, RB, R, R′, R″ is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
Type: Application
Filed: May 11, 2021
Publication Date: Dec 9, 2021
Applicant: UNIVERSAL DISPLAY CORPORATION (Ewing, NJ)
Inventors: Alexey Borisovich DYATKIN (Ambler, PA), Geza SZIGETHY (Newtown, PA), Jui-YI TSAI (Newtown, PA), Pierre-Luc T. BOUDREAULT (Pennington, NJ), Joseph A. MACOR (Morrisville, PA), Neil PALMER (Frenchtown, NJ)
Application Number: 17/316,895
