Organic electroluminscent materials and devices

Abstract

To provide a metal coordination complex compound that exhibits superior performance as an emitter for optoelectronic devices, or formulations, OLEDs, and consumer products comprising the same.SOLUTION: This metal coordination complex compound is capable of functioning as an emitter in an organic light emitting device (OLED) at a room temperature, and has a vertical dipole ratio (VDR) greater than 0.33 in the OLED.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure generally relates to organometallic compounds and formulations and their various uses, including use as emitters in devices such as organic light emitting diodes and related electronic devices.

Background Art

[0002] Optoelectronic devices that utilize organic materials are becoming increasingly desirable for various reasons. Many of the materials used to fabricate such devices are relatively inexpensive, so organic optoelectronic devices have the potential for cost advantages over inorganic devices. In addition, due to the inherent properties of organic materials such as flexibility, the materials can be well-suited for specific applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials.

[0003] OLEDs utilize thin organic films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, lighting, and backlighting.

[0004] One use of emissive molecules is in full-color displays. The industry standard for such displays requires pixels that are adapted to emit specific colors referred to as "saturated" colors. In particular, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. Conventional liquid crystal display emission from a white backlight is filtered using absorption filters to produce red, green, and blue emission. A similar technique can be used with OLEDs. White OLEDs can be either single layer emissive layer (EML) devices or laminated structures. Color can be measured using CIE coordinates well-known in the art.

Summary of the Invention

[0005] In some OLED applications, novel metal coordination complex compounds capable of functioning as emitters in organic light-emitting devices (OLEDs) at room temperature are disclosed. The compound includes a first emissive ligand coordinated to a metal; The compound has a vertical dipole ratio (VDR) greater than 0.33; At least one of the following is true: (1) The emissive ligand has a spin density population greater than 60%; (2) The emissive ligand has a natural transition orbital particle population greater than 50%; (3) The emissive ligand has a ligand-centered character (LC) greater than 30%; (4) The emissive ligand has a ligand-to-ligand charge transfer (LLCT) of less than 40%; (5) The emissive ligand has an M / T ratio greater than 0.42.

[0006] In another aspect, the present disclosure provides a formulation comprising the metal coordination complex compound described herein.

[0007] In yet another aspect, the present disclosure provides an OLED having an organic layer comprising the metal coordination complex compound described herein.

[0008] In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising the metal coordination complex compound described herein.

Brief Description of the Drawings

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Figure 1

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Figure 2

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Figure 3

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Figure 4

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Figure 5

DETAILED DESCRIPTION OF THE INVENTION

[0014] A. Terms Unless otherwise specified, the following terms used herein are defined as follows.

[0015] As used herein, the term "organic" includes polymeric materials and small molecule organic materials that can be used in the manufacture of organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and a "small molecule" can actually be quite large. Small molecules can include repeating units in some situations. For example, the use of a long-chain alkyl group as a substituent does not exclude a molecule from the "small molecule" class. Small molecules may also be incorporated into a polymer, for example as a pendant group on a polymer backbone or as part of the backbone. Small molecules can also function as the core portion of a dendrimer consisting of a series of chemical shells built on the core portion. The core portion of the dendrimer may be a small molecule emitter that fluoresces or phosphoresces. A dendrimer may be a "small molecule", and all dendrimers currently used in the field of OLEDs are considered to be small molecules.

[0016] As used herein, "top" means the farthest from the substrate, while "bottom" means the closest to the substrate. When a first layer is described as being "disposed on" a second layer, the first layer is disposed farther from the substrate. There may be other layers between the first layer and the second layer unless it is specified that the first layer is "in contact with" the second layer. For example, the cathode can be described as being "disposed on" the anode even if there are various organic layers in between.

[0017] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from any liquid medium in the form of a solution or suspension.

[0018] A ligand can be called "photoactive" if it is considered to directly contribute to the photoactive properties of a luminescent material. A ligand can be called "auxiliary" if it is considered not to contribute to the photoactive properties of a luminescent material, although an auxiliary ligand can change the properties of a photoactive ligand.

[0019] As used herein, and as generally understood by those skilled in the art, the first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy level is "greater" or "higher" than the second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). In 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 to be closer to the top of such a diagram than a "lower" HOMO or LUMO energy level.

[0020] As used herein, and as generally understood by those skilled in the art, if the first work function has a higher absolute value, the first work function is "greater" or "higher" than the second work function. Since the work function is generally measured as a negative number relative to the vacuum level, this means that a "higher" work function is more negative. In a conventional energy level diagram with the vacuum level at the top, a "higher" work function is illustrated as being further away in the downward direction from the vacuum level. Thus, the definitions of the HOMO and LUMO energy levels follow a different convention than the work function.

[0021] The terms "halo", "halogen", and "halide" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0022] The term "acyl" refers to a substituted carbonyl group (C(O)-R s ).

[0023] The term "ester" refers to a substituted oxycarbonyl (-O-C(O)-R s or -C(O)-O-Rs refers to a group.

[0024] The term "ether" refers to an -OR s group.

[0025] The terms "sulfanyl" or "thioether" are used interchangeably and refer to an -SR s group.

[0026] The term "selenyl" refers to an -SeR s group.

[0027] The term "sulfinyl" refers to an -S(O)-R s group.

[0028] The term "sulfonyl" refers to an -SO2-R s group.

[0029] The term "phosphino" refers to a -P(R s )2 group, where each R s may be the same or different.

[0030] The term "silyl" refers to a -Si(R s )3 group, where each R s may be the same or different.

[0031] The term "germyl" refers to a -Ge(R s )3 group, where each R s may be the same or different.

[0032] The term "boryl" refers to a -B(R s )2 group or its Lewis adduct -B(R s )3 group, where R s may be the same or different.

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

[0034] The term "alkyl" refers to and includes both straight-chain and branched-chain alkyl groups. Preferred alkyl groups are those having 1 to 15 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, etc. Further, the alkyl group may be optionally substituted.

[0035] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. Further, the cycloalkyl group may be optionally substituted.

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

[0037] The term "alkenyl" refers to and includes both straight-chain and branched-chain alkene groups. An alkenyl group is essentially an alkyl group containing at least one carbon-carbon double bond in the alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group containing at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group having at least one carbon atom replaced by a heteroatom. Optionally, 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 contain from 2 to 15 carbon atoms. Further, the alkenyl, cycloalkenyl, or heteroalkenyl group may be optionally substituted.

[0038] The term "alkynyl" refers to and includes both straight-chain and branched-chain alkyne groups. An alkynyl group is essentially an alkyl group containing at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups contain from 2 to 15 carbon atoms. Further, the alkynyl group may be optionally substituted.

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

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

[0041] The term "aryl" refers to and includes both monocyclic aromatic hydrocarbyl groups and polycyclic aromatic ring systems. The polycycle can have two or more rings in which two adjacent rings (these rings are "fused") share two carbons, where at least one of these rings is an aromatic hydrocarbon group, and for example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocycle, and / or heteroaryl. Preferred aryl groups are those containing 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Particularly preferred are aryl groups having 6, 10, or 12 carbon atoms. 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. Further, the aryl group may optionally be substituted.

[0042] The term "heteroaryl" refers to and includes both monocyclic aromatic groups and polycyclic aromatic ring systems containing at least one heteroatom. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many instances, O, S, or N are preferred heteroatoms. The hetero monocyclic aromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring can have from 1 to 6 heteroatoms. The hetero polycyclic ring system can have two or more rings where two atoms are common to two adjacent rings (the rings are "fused"), and at least one of these rings is heteroaryl, for example, the other rings can be cycloalkyl, cycloalkenyl, aryl, heterocycle, and / or heteroaryl. The hetero polycyclic aromatic ring system can have from 1 to 6 heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from 3 to 30 carbon atoms, preferably from 3 to 20 carbon atoms, more preferably from 3 to 12 carbon atoms.Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, 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 their aza analogs are included. Further, the heteroaryl group may be optionally substituted.

[0043] Among 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 their respective aza analogs are of particular interest.

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

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

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

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

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

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

[0050] As used herein, "their combinations" indicates that one or more members of the applied list are combined to form known or chemically stable arrangements that can be envisioned by one of ordinary skill in the art from the applied list. For example, alkyl and deuterium can be combined to form a partially or fully deuterated alkyl group; halogen and alkyl can be combined to form a halogenated alkyl substituent; and halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one example, the term substitution includes combinations of 2 to 4 of the listed groups. In another example, the term substitution includes combinations of 2 to 3 groups. In yet another example, the term substitution includes combinations of 2 groups. Preferred combinations of substituents are those containing up to 50 atoms other than hydrogen or deuterium, or those containing up to 40 atoms other than hydrogen or deuterium, or those containing up to 30 atoms other than hydrogen or deuterium. In many examples, preferred combinations of substituents contain up to 20 atoms other than hydrogen or deuterium.

[0051] As used herein, the term "aza" in fragments described herein, i.e., aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the C-H groups in each aromatic ring can be replaced by a nitrogen atom. For example, without limitation, azatriphenylene includes 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 above-described aza derivatives, and it is intended that all such analogs be encompassed by the terms described herein.

[0052] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, International Publication No. WO2006 / 095951, and U.S. Patent Application Publication No. 2011 / 0037057, the entire contents of which are incorporated by reference, describe the preparation of organometallic complexes substituted with deuterium. Further references are made by Tetrahedron 2015, 71, 1425 - 30 (Ming Yan et al.) and Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744 - 65 (Atzrodt et al.), the entire contents of which are incorporated by reference, which describe the deuteration of methylene hydrogens in benzylamine and an efficient route for replacing aromatic ring hydrogens with deuterium, respectively.

[0053] It should be understood that when a molecular fragment is described as being a substituent or as being attached to another moiety, its name may be described as being a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these are considered equivalent even if the manner of representation of the substituent or attached fragment is different.

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

[0055] B. Compounds of the Present Disclosure In some OLED applications, novel metal coordination complex compounds capable of functioning as emitters in an organic light-emitting device (OLED) at room temperature are disclosed. The compounds include a first emissive ligand coordinated to a metal; the compounds have a vertical dipole ratio (VDR) greater than 0.33; at least one of the following is true: (1) The first emissive ligand has a spin density population greater than 60%; (2) The first emissive ligand has a natural transition orbital (NTO) population greater than 50%; (3) The first emissive ligand has a ligand-centered character (LC) greater than 30%; (4) The first emissive ligand has a complex ligand-to-ligand charge transfer (LLCT) less than 40%; (5) The first emissive ligand has an M / T ratio greater than 0.42. It is a minimum requirement that at least one of the five conditions above is true for the compound, but any number of combinations of the five conditions may be true.

[0056] As used herein, room temperature is defined as about 22 °C (e.g., 22 °C ± 1 °C).

[0057] As used herein, "spin density" refers to the electron density applicable to free radicals and other open-shell structures. This is defined as the difference between the total electron density of the electrons of one spin and the total electron density of the electrons of the other spin.

[0058] The triplet spin density of the compound was calculated using density functional theory (DFT). The calculations were performed using the unrestricted B3LYP functional with the CEP-31G basis set. The geometric optimization of the first triplet excited state was carried out in vacuum with the spin multiplicity set to 3. Next, the spin density was calculated as the difference between the α-spin concentration and the β-spin concentration using the CubeGen utility of the Gaussian program. All calculations were performed using the Gaussian program. To determine the spin density populations of each atom and each atomic group, the spin density was subjected to Löwdin population analysis as described by Löwdin, P.-O. J. Chem. Phys. 1950, 18, 365 and Löwdin, P.-O. Adv Quantum Chem 1970, 5, 185. This is achieved by dividing the spin density into the contributions of discrete atom centers that collectively make up the molecule. These contributions are then collected individually or as groups as needed.

[0059] DFT calculations were performed to determine the energy of the lowest triplet excited state (T1) of the compound, the proportion of ligand-centered (LC) character, and the proportion of ligand-to-ligand charge transfer (LLCT) involved in T1. The data were collected using the Gaussian16 program. The geometric structure was optimized using the B3LYP functional and the CEP-31G basis set. The excited state energies were calculated by TDDFT with the optimized ground state geometric structure. To further improve the agreement with the experiment, the THF solvent was simulated using the self-consistent reaction field. The LC character and LLCT contributions were determined by transition density matrix analysis of the excited state.

[0060] The calculations obtained using the above DFT function sets and basis sets are theoretical. Computational composite protocols such as Gaussian16 using the B3LYP and CEP-31G protocols used herein rely on the assumption that electronic effects are additive, so larger basis sets can be used to extrapolate to the complete basis set (CBS) limit. However, if the goal of the study is to understand the variations in HOMO, LUMO, S1, T1, bond dissociation energy, etc. in a series of structurally related compounds, the additive effects are expected to be similar. Therefore, the absolute error due to using B3LYP can be significant compared to other calculation methods, but the relative differences between the HOMO, LUMO, S1, T1, and bond dissociation energy values calculated using the B3LYP protocol are expected to reproduce the experiment quite well. See, for example, Hong et al., Chem. Mater. 2016, 28, 5791-98, 5792-93 and Supplementary Information (discussing the reliability of DFT calculations in the context of OLED materials). Furthermore, for iridium or platinum complexes useful in OLED technology, the data obtained from DFT calculations correlates very well with actual experimental data. Tavasli et al., J. Mater. Chem. 2012, 22, 6419-29, 6422 (Table 3) (showing that DFT calculations and actual data are closely correlated for various luminescent complexes); Morello, G.R., J. Mol. Model. 2017, 23:174 (studying various DFT function sets and basis sets and concluding that the combination of B3LYP and CEP-31G is accurate, especially for luminescent complexes). The determination of excited state transition properties is performed as a post-processing step of the DFT and TDDFT calculations described above. This analysis allows the excited state to be decomposed into holes (i.e., the location where excitation starts) and electrons (i.e., the final location of the excited state). Furthermore, since this analysis is performed on the calculated properties, it is objective and reproducible; see Mai et al., Coord. Chem. Rev. 2018, 361, 74-97 (discussing the theoretical basis for excited state decomposition in transition metal complexes).

[0061] The natural transition orbit (NTO) is obtained from the singular value decomposition of the transition density matrix from the Gaussian16 program. The transition density matrix is obtained from TDDFT at the geometric structure of the ground state optimized using the B3LYP functional and the CEP-31G basis set. The THF solvent was simulated using the self-consistent reaction field. The hole NTO is the orbit obtained by the unitary transformation of the occupied molecular orbitals. The particle NTO is the orbit obtained by the unitary transformation of the virtual molecular orbitals and represents the position of the excited electrons. The NTO hole / particle populations of atoms and each atomic group are obtained from Löwdin population analysis.

[0062] The M / T ratio is calculated from the emission spectrum of the OLED emitter. M is the area of the main peak, which is defined as the integral of the area with a maximum peak wavelength (λ max ) ± 15 nm and T is the total area of the spectrum (normalized intensity) between the points where the intensity of the spectrum is 0.1%. A high M / T ratio means that the line shape of the dopant is narrow (i.e., most of the emission spectrum is part of the main peak). To determine the M / T ratio, a thin film is prepared by depositing the same composition and thickness as used in the emission region of the OLED on a quartz substrate. The emission spectrum of the thin film is measured at an excitation wavelength of 340 nm using a Hamamatsu Photonics Quantaurus-QY Plus UV-NIR absolute PL quantum yield spectrometer.

[0063] The vertical dipole ratio (VDR) is the ensemble average fraction of dipoles in a sample oriented perpendicular to the substrate plane (the vertical and the normal to the substrate are the same). As a similar concept, the horizontal dipole ratio (HDR) is the ensemble average fraction of dipoles oriented horizontally with respect to the substrate plane. By definition, VDR + HDR = 1. The VDR can be measured by angle dependence, polarization dependence, and photoluminescence measurement. The VDR of the light-emitting layer can be determined by comparing the measured emission pattern of the photoexcited thin film sample, as a function of polarization, with the modeled pattern by calculation. For example, the modeled data of p-polarized emission are shown in FIG. 3. The modeled p-polarization angle photoluminescence (PL) is plotted for emitters with different VDRs. The peak of the modeled PL is observed in the p-polarized PL near the angle of 45 degrees, and the higher the VDR of the emitter, the larger the peak PL becomes.

[0064] In this example used for the creation of FIG. 3, there is a film with a thickness of 30 nm of a material with a refractive index of 1.75, and the emission is monitored in a semi-infinite medium with a refractive index of 1.75. Each curve is normalized with the photoluminescence intensity at an angle of 0 degrees perpendicular to the film surface being 1. When the VDR of the emitter changes, the peak near 45 degrees increases significantly. When fitting the VDR of the experimental data using software, the modeled VDR changes until the difference between the modeled data and the experimental data is minimized.

[0065] Importantly, the VDR represents the average dipole orientation of the luminescent compound. Thus, if there are additional emitters in the emissive layer that do not contribute to luminescence, the VDR measurement will not report or reflect their VDRs. Further, by including a host that interacts with the emitter, the VDR of a given emitter can be altered, and as a result, the VDRs of layers with emitters in different hosts can be measured. Additionally, in some embodiments, an exciplex or excimer that forms an emissive state between two adjacent molecules is desirable. These emissive states can have a different VDR than when only one of the components of the exciplex or excimer is emitting or when present in the sample.

[0066] The emitter emits light in a direction perpendicular to its transition dipole moment (TDM) vector, which aligns with the electric field vector of the resulting light wave. Thus, in conventional OLEDs, it is desirable for the TDM vectors of the emitters to be highly horizontally aligned in order to emit light in a direction perpendicular to the substrate towards the observer. This maximizes the out-coupling of light and minimizes efficiency loss mechanisms such as light guiding in the OLED or substrate, or plasmon coupling. Plasmon coupling has conventionally been a major limitation to OLED efficiency and has been designed to be avoided in the art by sacrificing device voltage to move the emitter away from the cathode.

[0067] For the reasons above, vertically aligned emitters, i.e., emitters with a high VDR, have not been widely studied or applied in the field of OLEDs simply because they are contrary to the excellent design objectives of conventional OLED devices. Currently, it has been found that highly plasmonic coupling is desirable in carefully designed plasmonic OLEDs. Thus, in this situation, high-VDR emitters can be used to increase the rate or yield of plasmon coupling and improve the efficiency of plasmonic OLEDs.

[0068] In some embodiments, the OLED is a plasmonic OLED. In some embodiments, the OLED is a waveguide OLED.

[0069] In some embodiments, the compound has a VDR of 0.35 or more. In some embodiments, the compound has a VDR of 0.4 or more. In some embodiments, the compound has a VDR of 0.45 or more. In some embodiments, the compound has a VDR of 0.5 or more. In some embodiments, the compound has a VDR of 0.6 or more. In some embodiments, the compound has a VDR of 0.7 or more. In some embodiments, the compound has a VDR of 0.8 or more. In some embodiments, the compound has a VDR of 0.9 or more.

[0070] In some embodiments of the metal coordination complex compounds of the present disclosure, at least two of the conditions (1)-(5) listed above are true. In some embodiments, at least three of the conditions (1)-(5) are true. In some embodiments, at least four of the conditions (1)-(5) are true.

[0071] In some embodiments, the first luminescent ligand has a spin density population greater than 60%. In some embodiments, the first luminescent ligand has a spin density population greater than 70%. In some embodiments, the first luminescent ligand has a spin density population greater than 80%. In some embodiments, the first luminescent ligand has a spin density population greater than 90%. In some embodiments, the first luminescent ligand has a spin density population greater than 95%.

[0072] In some embodiments, the first luminescent ligand has a NTO particle population greater than 50%. In some embodiments, the first luminescent ligand has a NTO particle population greater than 60%. In some embodiments, the first luminescent ligand has a NTO particle population greater than 70%. In some embodiments, the first luminescent ligand has a NTO particle population greater than 80%. In some embodiments, the first luminescent ligand has a NTO particle population greater than 90%.

[0073] In some embodiments, the first luminescent ligand has an LC greater than 30%. In some embodiments, the first luminescent ligand has an LC greater than 40%. In some embodiments, the first luminescent ligand has an LC greater than 50%. In some embodiments, the first luminescent ligand has an LC greater than 60%. In some embodiments, the first luminescent ligand has an LC greater than 70%. In some embodiments, the first luminescent ligand has an LC greater than 80%. In some embodiments, the first luminescent ligand has an LC greater than 90%.

[0074] In some embodiments, the first luminescent ligand has a composite LLCT less than 40%. In some embodiments, the first luminescent ligand has a composite LLCT less than 30%. In some embodiments, the first luminescent ligand has a composite LLCT less than 20%. In some embodiments, the first luminescent ligand has a composite LLCT less than 10%.

[0075] In some embodiments, the first luminescent ligand has an M / T ratio greater than 0.42. In some embodiments, the first luminescent ligand has an M / T ratio greater than 0.44. In some embodiments, the first luminescent ligand has an M / T ratio greater than 0.46. In some embodiments, the first luminescent ligand has an M / T ratio greater than 0.48. In some embodiments, the first luminescent ligand has an M / T ratio greater than 0.50.

[0076] In some embodiments, the first luminescent ligand includes a polycyclic condensed ring system that coordinates to a metal.

[0077] In some of these embodiments, the polycyclic fused ring system comprises at least three fused rings. In some embodiments, the polycyclic fused ring structure has two 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to Ir, and the second 6-membered ring is fused to the 5-membered ring. In some embodiments, the polycyclic fused ring system is selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and their aza-variants. In some such embodiments, moiety E may be further substituted at the ortho or meta position of the O, S, or Se atom with a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the aza-variant contains exactly one N atom at the 6-position (ortho to O, S, or Se) and has a substituent at the 7-position (meta to O, S, or Se).

[0078] In some of these embodiments, the polycyclic fused ring structure comprises at least four fused rings. In some embodiments, the polycyclic fused ring structure comprises three 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to Ir, the second 6-membered ring is fused to the 5-membered ring, and the third 6-membered ring is fused to the second 6-membered ring. In some such embodiments, the third 6-membered ring is further substituted with a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0079] In some of these embodiments, the polycyclic fused ring structure comprises at least 5 fused rings. In some embodiments, the polycyclic fused ring structure comprises 4 six-membered rings and 1 five-membered ring or 3 six-membered rings and 2 five-membered rings. In some embodiments comprising 2 five-membered rings, the five-membered rings are fused together. In some embodiments comprising 2 five-membered rings, the five-membered rings are separated by at least 1 six-membered ring. In some embodiments having 1 five-membered ring, the five-membered ring is fused to the ring coordinated to Ir, the second six-membered ring is fused to the five-membered ring, the third six-membered ring is fused to the second six-membered ring, and the fourth six-membered ring is fused to the third six-membered ring.

[0080] In some of these embodiments, the polycyclic fused ring structure comprises an aza-version of the above fused rings. In some such embodiments, the polycyclic fused ring structure comprises exactly 1 aza N atom. In some such embodiments, the polycyclic fused ring structure comprises exactly 2 aza N atoms, which may be present in 1 ring or 2 different rings. In some such embodiments, the ring having an aza N atom is separated from the Ir atom by at least 2 other rings. In some such embodiments, the ring having an aza N atom is separated from the Ir atom by at least 3 other rings. In some such embodiments, each ortho-position of the aza N atom is substituted.

[0081] In some embodiments, the compound further comprises a second ligand coordinated to the metal; and / or each of the luminescent ligand and the second ligand has an effective length, and the effective length of the luminescent ligand is at least 3 Å greater than the effective length of the second ligand; and / or the luminescent ligand has at least 5 more non-hydrogen atoms than the second ligand, and / or the luminescent ligand has a molecular weight that is at least 100 amu greater than the molecular weight of the second ligand; and / or the luminescent ligand has at least 3 more aliphatic methylene carbons than the second ligand.

[0082] In some embodiments, the compound further comprises a second ligand coordinated to the metal; the compound has a first free vector F1 represented by a binding vector M1 that connects any two atoms in the compound and passes within 2 Å of the metal, and the length of the binding vector M1 is greater than 18 Å; the compound has a second free vector F2 represented by a binding vector M2 that connects any two atoms in the compound; the length of the binding vector M2 is greater than 18 Å; the compound has a transition dipole moment vector, and the angle between the transition dipole moment vector and the cross product of the vectors F1 and F2 is less than 45 degrees. The transition dipole moment vector is the transition dipole moment vector on the emissive ligand.

[0083] Compound

Chemical formula

Table 1

[0084] From this perspective, the atomic coordinates were determined using the lowest energy structure of the triplet state with spin constrained on the emissive ligand, which was performed using the LACVP * basis set and DFT in the B3LYP functional. The transition dipole moment (TDM) is then calculated using this geometric structure.

[0085] In Table 2, the "maximum ┴ distance (Å) from plane P" means the maximum perpendicular distance of an atom from plane P.

[0086] In some embodiments, the second free vector F2 forms an angle greater than 45 degrees with the first free vector F1.

[0087] When multiple atom pairs satisfy the requirements of the first binding vector M1, the pair that forms the longest first binding vector satisfying other requirements is selected. When multiple atom pairs satisfy the requirements of the second binding vector M2, the pair that forms the longest second binding vector satisfying other requirements is selected.

[0088] In some embodiments, the complex compound has a first free vector F1 represented by a first binding vector M1 that connects any two atoms in the compound, passes within 1 Å of a metal, and has a length exceeding 18 Å; the compound has a second free vector F2 represented by a second binding vector M2 that connects any two atoms in the compound and has a length exceeding 18 Å; the angle between the luminescent transition dipole moment vector and the outer product of vectors F1 and F2 is less than 45 degrees.

[0089] In some embodiments, the atoms forming the second binding vector M2 are within the same ligand, and the atoms forming the first binding vector M1 are within different ligands. In some embodiments, the atoms forming the second binding vector M2 are within a ligand different from any of the atoms forming the first binding vector M1.

[0090] In some embodiments, the second vector F2 forms an angle greater than 45 degrees with F1.

[0091] In some embodiments of the second aspect, the second vector F2 is the longest vector that connects any two atoms in the molecule and forms an angle greater than 60 degrees with F1.

[0092] In some embodiments of the second aspect, the lengths of F1 and F2 both exceed 20 Å. In some embodiments of the second aspect, the lengths of F1 and F2 both exceed 22 Å.

[0093] In some embodiments, the angle between the luminescent transition dipole moment vector and the cross product of the vectors F1 and F2 is less than 30 degrees. In some embodiments, the angle between the luminescent transition dipole moment vector and the cross product of the vectors F1 and F2 is less than 20 degrees.

[0094] In some embodiments, the compound has a plane P defined by free vectors F1 and F2 represented by corresponding binding vectors M1 and M2, the plane P is parallel to M1 and M2 and passes through the metal M; the sum of the perpendicular distance from the plane P to the farthest atom above the plane P and the perpendicular distance from the plane P to the farthest atom below the plane P is less than 14 Å. In some such embodiments, the sum of the perpendicular distance from the plane P to the farthest atom above the plane P and the perpendicular distance from the plane P to the farthest atom below the plane P is less than 12 Å. In some such embodiments, the sum of the perpendicular distance from the plane P to the farthest atom above the plane P and the perpendicular distance from the plane P to the farthest atom below the plane P is less than 10 Å.

[0095] The perpendicular distance from the plane P is calculated using the standard formula for the distance of a point from a plane:

Equation

[0096] In some embodiments, the compound comprises a first ligand and a second ligand, each coordinated to a metal. In some embodiments of such compounds, the compound can have two metal-donor bonds in a trans configuration; the compound has a first vector W1 formed between any atom around the compound and the metal; the compound has a second vector W2 formed between any other atom around the compound and the metal; the magnitude of each of W1 and W2 is greater than 9.5 Å; the compound has a luminescent transition dipole moment vector, and the angle between the luminescent transition dipole moment vector and the cross product of the vectors W1 and W2 is less than 45 degrees.

[0097] In some embodiments, the compound has a transition dipole moment vector, and the compound is a four-coordinate square plane in which the transition dipole moment vector is deviated by 45 degrees or more from a reference plane defined by at least three atoms around ligands that are at least 8 Å apart from each other.

[0098] In some embodiments, the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu.

[0099] In some embodiments, the compound has the formula M(L A ) p (L B ) q (L C ) r wherein L A is a luminescent ligand; L B and L C are each bidentate ligands; 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).

[0100] In some embodiments where the compound has the formula M(L A ) p (L B ) q (L C ) r the compound is Ir(L A) 3. Ir(L A )(L B ) 2. Ir(L A ) 2 (L B )、Ir(L A ) 2 (L C )、and Ir(L A )(L B )(L C ) and can have a formula selected from the group consisting of; in the formula, L A , L B , and L C are different from each other. In some embodiments, the compound is M(L A ) p (L B ) q (L C ) r of the formula, wherein L A has the structure of formula I: [Chemical formula] (wherein moieties A and B are each independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; Z 1 ~Z 4 are each independently C or N; K 1 and K 2 are each independently a direct bond, O, S, N(R α ), P(R α ), B(R α ), C(R α )(R β ), and Si(R α )(R β ) selected from the group consisting of; L 1 is selected from the group consisting of a direct bond, BR, BRR’, NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR’, C=CRR’, S=O, SO2, CR, CRR’, SiRR’, and GeRR’; R A and R Beach independently represents a substitution from mono-substitution to the maximum allowable number of substitutions, or no substitution; each R, R’, R α , R β , R A , and R B is independently a hydrogen, or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof); L A is coordinated to the metal M; M is coordinated to at least one auxiliary ligand; L A can combine with one or more additional ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand; and any two substituents can be bonded or condensed to form a ring.

[0101] In some embodiments of Formula I, at least one of moiety A or B has a fused ring system containing four or more 5- and / or 6-membered carbocyclic or heterocyclic rings.

[0102] In some embodiments of Formula I, each R, R’, R α , R β , R A , and R B is independently a hydrogen, or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

[0103] In some embodiments of Formula I, the ligand L Ahas the structure of Formula I. In some embodiments, ligand L A has a structure that consists essentially of the structure of Formula I.

[0104] In some embodiments of Formula I, moieties A and B in Formula I are each independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- or 6-membered carbocyclic or heterocyclic ring. In some embodiments, each of moieties A and B is independently aryl or heteroaryl.

[0105] In some embodiments of Formula I, R A or R B is at least partially or fully deuterated. In some embodiments, at least one R A is at least partially or fully deuterated. In some embodiments, at least one R B is at least partially or fully deuterated. In some embodiments, at least one R or R' is at least partially or fully deuterated.

[0106] In some embodiments of Formula I, each of moiety A and moiety B is independently a moiety of the following list of cyclic moieties: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, benzimidazole-derived carbene, aza-benzimidazole, aza-benzimidazole-derived carbene, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene, selected from the group consisting of.

[0107] In some embodiments of Formula I, the aza-variant contains one N on the benzo ring. In some embodiments, the aza-variant contains one N on the benzo ring and the N is bonded to metal M.

[0108] In some embodiments of Formula I, moiety A is a monocyclic ring.

[0109] In some embodiments of Formula I, moiety A is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.

[0110] In some embodiments of Formula I, moiety A is pyridine, pyrazole, imidazole, or an imidazole-derived carbene. In some embodiments, moiety A is a polycyclic fused ring system. In some embodiments, moiety A is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, benzimidazole-derived carbene, aza-benzimidazole, aza-benzimidazole-derived carbene, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

[0111] In some embodiments of Formula I, moiety A is a polycyclic fused ring containing three 5- or 6-membered carbocyclic or heterocyclic rings. In some embodiments, moiety A is quinoline, isoquinoline, indazole, benzimidazole, or a benzimidazole-derived carbene. In some embodiments, moiety A is a polycyclic fused ring containing at least four 5- or 6-membered carbocyclic or heterocyclic rings.

[0112] In some embodiments of Formula I, moiety A includes moiety A1 cyclized by moiety A2, moiety A1 includes Z 1 and each of moiety A1 and moiety A2 is independently selected from the group consisting of moieties in the cyclic moiety list.

[0113] In some embodiments of Formula I, moiety A1 is selected from the group consisting of aza-carbazole, aza-dibenzofuran, aza-dibenzothiophene, quinoxaline, phthalazine, aza-phenanthrene, aza-anthracene, phenanthridine, and aza-fluorene.

[0114] In some embodiments of Formula I, moiety A2 is benzene or naphthalene.

[0115] In some embodiments of Formula I, moiety B is a monocyclic ring. In some embodiments, moiety B is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, moiety B is benzene. In some embodiments, moiety B is a polycyclic fused ring system.

[0116] In some embodiments of Formula I, moiety B is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, benzimidazole-derived carbene, aza-benzimidazole, aza-benzimidazole-derived carbene, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

[0117] In some embodiments of Formula I, moiety B is a polycyclic fused ring containing three 5- or 6-membered carbocyclic or heterocyclic rings.

[0118] In some embodiments of Formula I, moiety B is carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthrene, anthracene, phenanthridine, and fluorene.

[0119] In some embodiments of Formula I, moiety B is a polycyclic fused ring comprising at least four 5- or 6-membered carbocyclic or heterocyclic rings.

[0120] In some embodiments of Formula I, moiety B comprises moiety B1 which is cyclized by moiety B2, and moiety B1 comprises Z 2 and each of moiety B1 and moiety B2 is independently selected from the group consisting of moieties in the cyclic moiety list.

[0121] In some embodiments of Formula I, moiety B1 is selected from the group consisting of carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

[0122] In some embodiments of Formula I, moiety B2 is benzene or naphthalene. In some embodiments, moiety B2 is dibenzofuran or naphthalene.

[0123] In some embodiments of Formula I, Z 1 is N and Z 2 is C. In some embodiments, Z 1 is a carbene carbon and Z 2 is C.

[0124] In some embodiments of Formula I, each of Z 2 ~Z 4 is C. In some embodiments, at least one of Z 2 ~Z 4 is N.

[0125] In some embodiments of Formula I, each of K 1 and K 2 is a direct bond. In some embodiments, at least one of K 1 or K 2 is not a direct bond. In some embodiments, K 1 or K2 Exactly one of them is not a direct bond. In some embodiments, K 1 is not a direct bond and Z 1 is C. In some embodiments, K 2 is not a direct bond and Z 2 is C. In some embodiments, K 1 is a direct bond. In some embodiments, K 1 is O or S. In some embodiments, K 1 is O. In some embodiments, K 1 is S.

[0126] In some embodiments of Formula I, K 1 is selected from the group consisting of N(R α ), P(R α ), and B(R α ). In some embodiments, K 1 is selected from the group consisting of C(R α )(R β ) and Si(R α )(R β ).

[0127] In some embodiments of Formula I, K 2 is a direct bond. In some embodiments, K 2 is O or S. In some embodiments, K 2 is O. In some embodiments, K 2 is S.

[0128] In some embodiments of Formula I, K 2 is selected from the group consisting of N(R α ), P(R α ), and B(R α ). In some embodiments, K 2 is selected from the group consisting of C(R α )(R β ) and Si(R α )(R β ).

[0129] For L in Formula I AIn some embodiments of the compounds having A the ligand L is an electron withdrawing group selected from the group consisting of the following EWG1 list: F, CF3, CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, + N(R k2 )3, (R k2 )2CCN, (R k2 )2CCF3, CNC(CF3)2, BR k3 R k2 , substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridoxine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano group-containing alkyl, cyano group-containing aryl, cyano group-containing heteroaryl, isocyanate,

Chemical formula

[0130] In some embodiments of the compound having L of formula I A the ligand L A has a structure of the following EWG2 list:

Chemical formula

Chemical formula

[0131] In some embodiments of the compound having L of formula I A the ligand L A has a structure of the following EWG3 list:

Chemical formula

[0132] In some embodiments of the compound having L of formula I A the ligand L A has a structure of the following EWG4 list:

Chemical formula

[0133] L of formula I A In some embodiments of the compound having A the ligand L contains an electron-withdrawing group that is a π-electron-deficient electron-withdrawing group. In some embodiments, the π-electron-deficient electron-withdrawing group has the structure of the following Pi-EWG list: CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, + N(R k2 )3, BR k2 R k3 , substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridazine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano group-containing aryl, cyano group-containing heteroaryl, isocyanate, [Chemical formula] (wherein the variables are the same as those defined above) and is selected from the group consisting of.

[0134] L of formula I A In some embodiments of the compound having α R, R', R β R A , and RB At least one of them is, or includes, an electron-withdrawing group from the EWG1 list defined herein. In some embodiments, R, R', R α , R β , R A , and R B At least one of them is, or includes, an electron-withdrawing group from the EWG2 list defined herein. In some embodiments, R, R', R α , R β , R A , and R B At least one of them is, or includes, an electron-withdrawing group from the EWG3 list defined herein. In some embodiments, R, R', R α , R β , R A , and R B At least one of them is, or includes, an electron-withdrawing group from the EWG4 list defined herein. In some embodiments, R, R', R α , R β , R A , and R B At least one of them is, or includes, an electron-withdrawing group from the Pi-EWG list defined herein.

[0135] In some embodiments of the compounds having L A of Formula I, at least one of R A is, or includes, an electron-withdrawing group from the EWG1 list defined herein. In some embodiments, at least one of R A is, or includes, an electron-withdrawing group from the EWG2 list defined herein. In some embodiments, at least one of R A is, or includes, an electron-withdrawing group from the EWG3 list defined herein. In some embodiments, at least one of R A is, or includes, an electron-withdrawing group from the EWG4 list defined herein. In some embodiments, at least one of R AAt least one of them is or contains an electron-withdrawing group from the Pi-EWG list defined herein.

[0136] L of formula I A In some embodiments of the compounds having B at least one of R is or contains an electron-withdrawing group from the EWG1 list defined herein. In some embodiments, R B at least one of is or contains an electron-withdrawing group from the EWG2 list defined herein. In some embodiments, R B at least one of is or contains an electron-withdrawing group from the EWG3 list defined herein. In some embodiments, R B at least one of is or contains an electron-withdrawing group from the EWG4 list defined herein. In some embodiments, R B at least one of is or contains an electron-withdrawing group from the Pi-EWG list defined herein.

[0137] L of formula I A In some embodiments of the compounds having, R is or contains an electron-withdrawing group from the EWG1 list defined herein. In some embodiments, R is or contains an electron-withdrawing group from the EWG2 list defined herein. In some embodiments, R is or contains an electron-withdrawing group from the EWG3 list defined herein. In some embodiments, R is or contains an electron-withdrawing group from the EWG4 list defined herein. In some embodiments, R is or contains an electron-withdrawing group from the Pi-EWG list defined herein.

[0138] L of formula I AIn some embodiments of the compounds having, R’ is an electron withdrawing group from the EWG1 list as defined herein or includes it. In some embodiments, R’ is an electron withdrawing group from the EWG2 list as defined herein or includes it. In some embodiments, R’ is an electron withdrawing group from the EWG3 list as defined herein or includes it. In some embodiments, R’ is an electron withdrawing group from the EWG4 list as defined herein or includes it. In some embodiments, R’ is an electron withdrawing group from the Pi-EWG list as defined herein or includes it.

[0139] L of formula I A In some embodiments of the compounds having α R is an electron withdrawing group from the EWG1 list as defined herein or includes it. In some embodiments, R α is an electron withdrawing group from the EWG2 list as defined herein or includes it. In some embodiments, R α is an electron withdrawing group from the EWG3 list as defined herein or includes it. In some embodiments, R α is an electron withdrawing group from the EWG4 list as defined herein or includes it. In some embodiments, R α is an electron withdrawing group from the Pi-EWG list as defined herein or includes it.

[0140] L of formula I A In some embodiments of the compounds having β R is an electron withdrawing group from the EWG1 list as defined herein or includes it. In some embodiments, R β is an electron withdrawing group from the EWG2 list as defined herein or includes it. In some embodiments, R β is an electron withdrawing group from the EWG3 list as defined herein or includes it. In some embodiments, R βis an electron-withdrawing group from the EWG4 list as defined herein, or comprises the same. In some embodiments, R β is an electron-withdrawing group from the Pi-EWG list as defined herein, or comprises the same.

[0141] In some embodiments of the compound having L of Formula I A at least one R A or R B comprises an electron-withdrawing group other than F.

[0142] In some embodiments of the compound having L of Formula I A at least one R A comprises an electron-withdrawing group other than F.

[0143] In some embodiments of the compound having L of Formula I A at least one R B comprises an electron-withdrawing group other than F.

[0144] In some embodiments of the compound having L of Formula I A at least two in total of R A and R B independently comprise an electron-withdrawing group other than F.

[0145] In some embodiments of the compound having L of Formula I A at least one R A is an electron-withdrawing group other than F selected from the EWG1 list as defined herein, or comprises the same. In some embodiments, R A is an electron-withdrawing group other than F selected from the EWG1 list as defined herein. In some embodiments, R A comprises an electron-withdrawing group other than F selected from the EWG1 list as defined herein.

[0146] In some embodiments of the compound having L of Formula I A at least one R Ais an electron-withdrawing group other than F selected from the EWG2 list defined herein, or comprises the same. In some embodiments, R A is an electron-withdrawing group other than F selected from the EWG2 list defined herein. In some embodiments, R A comprises an electron-withdrawing group other than F selected from the EWG2 list defined herein.

[0147] In some embodiments of the compounds having L of Formula I A at least one R A is an electron-withdrawing group other than F selected from the EWG3 list defined herein, or comprises the same. In some embodiments, R A is an electron-withdrawing group other than F selected from the EWG3 list defined herein. In some embodiments, R A comprises an electron-withdrawing group other than F selected from the EWG3 list defined herein.

[0148] In some embodiments of the compounds having L of Formula I A at least one R A is an electron-withdrawing group other than F selected from the EWG4 list defined herein, or comprises the same. In some embodiments, R A is an electron-withdrawing group other than F selected from the EWG4 list defined herein. In some embodiments, R A comprises an electron-withdrawing group other than F selected from the EWG4 list defined herein.

[0149] In some embodiments of the compounds having L of Formula I A at least one R A is an electron-withdrawing group other than F selected from the Pi-EWG list defined herein, or comprises the same. In some embodiments, R A is an electron-withdrawing group other than F selected from the Pi-EWG list defined herein. In some embodiments, R A comprises an electron-withdrawing group other than F selected from the Pi-EWG list defined herein.

[0150] L of formula I A In some embodiments of the compounds having, at least one R B is an electron-withdrawing group other than F selected from the EWG1 list defined herein, or comprises it. In some embodiments, R B is an electron-withdrawing group other than F selected from the EWG1 list defined herein. In some embodiments, R B comprises an electron-withdrawing group other than F selected from the EWG1 list defined herein.

[0151] L of formula I A In some embodiments of the compounds having, at least one R B is an electron-withdrawing group other than F selected from the EWG2 list defined herein, or comprises it. In some embodiments, R B is an electron-withdrawing group other than F selected from the EWG2 list defined herein. In some embodiments, R B comprises an electron-withdrawing group other than F selected from the EWG2 list defined herein.

[0152] L of formula I A In some embodiments of the compounds having, at least one R B is an electron-withdrawing group other than F selected from the EWG3 list defined herein, or comprises it. In some embodiments, R B is an electron-withdrawing group other than F selected from the EWG3 list defined herein. In some embodiments, R B comprises an electron-withdrawing group other than F selected from the EWG3 list defined herein.

[0153] L of formula I A In some embodiments of the compounds having, at least one R B is an electron-withdrawing group other than F selected from the EWG4 list defined herein, or comprises it. In some embodiments, R Bis an electron-withdrawing group other than F selected from the EWG4 list defined herein. In some embodiments, R B comprises an electron-withdrawing group other than F selected from the EWG4 list defined herein.

[0154] In some embodiments of the compound having L of Formula I A at least one R B is an electron-withdrawing group other than F selected from the Pi-EWG list defined herein or comprises the same. In some embodiments, R B is an electron-withdrawing group other than F selected from the Pi-EWG list defined herein. In some embodiments, R B comprises an electron-withdrawing group other than F selected from the Pi-EWG list defined herein.

[0155] M(L A ) p (L B ) q (L C ) r In some embodiments of the compound having the formula of B the ligand L B comprises an electron-withdrawing group from the EWG1 list defined herein. In some embodiments, L B comprises an electron-withdrawing group from the EWG2 list defined herein. In some embodiments, L B comprises an electron-withdrawing group from the EWG3 list defined herein. In some embodiments, L B comprises an electron-withdrawing group from the EWG4 list defined herein. In some embodiments, L

[0156] M(L A ) p (L B ) q (L C ) r In some embodiments of the compound having the formula of Cincludes an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, L C includes an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, L C includes an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, L C includes an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, L C includes an electron-withdrawing group from the Pi-EWG list as defined herein.

[0157] In some embodiments of the compound having L of Formula I A at least one R A is not hydrogen. In some embodiments, at least one R A contains at least one C atom.

[0158] In some embodiments of the compound having L of Formula I A at least one R B is not hydrogen. In some embodiments, at least one R B contains at least one C atom.

[0159] In some embodiments of the compound having L of Formula I A L is a direct bond. In some embodiments, L is selected from the group consisting of O, S, and Se. In some embodiments, L is selected from the group consisting of BR, NR, and PR. In some embodiments, L is BR. In some embodiments, L is NR. In some embodiments, L is PR. In some embodiments, R is aryl or heteroaryl. In some embodiments, R is bonded or fused to one of R A or R B to form a ring, and this ring can be a 5-membered ring. In some embodiments, the 5-membered ring is a pyrrole ring.

[0160] In some embodiments of the compound having L of Formula I AIn some embodiments of the compounds having, L is selected from the group consisting of P(O)R, C=O, C=S, C=Se, C=NR’, C=CRR’, S=O, and SO2.

[0161] L of formula I A In some embodiments of the compounds having, L is selected from the group consisting of BRR’, CRR’, SiRR’, and GeRR’.

[0162] L of formula I A In some embodiments of the compounds having, L is CR.

[0163] L of formula I A In some embodiments of the compounds having, the ligand L A is

Chemical formula

Chemical formula

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Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0164] In some embodiments of the compound, ligand L A is

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0165] In some embodiments of the compound, ligand L A is LAi selected from, where i is an integer from 1 to 335; each L Ai is as defined below:

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

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Chemical formula

Chemical formula

[0166] M(L A ) p (L B ) q (L C ) r In some embodiments of the compounds having the formula M(L B ) C (L

[0167] M(L A ) p (L B ) q (L C ) r In some embodiments of the compounds having the formula M(L B and L C are each independently [Chemistry] [Chemical formula] (wherein, T is selected from the group consisting of B, Al, Ga, and In; K 1’ is a single bond, O, S, NR e , PR e , BR e , CR e R f , and SiR e R f selected from the group consisting of; Y 1 ~Y 13 each is independently selected from the group consisting of C and N; Y’ is BR e , BR e R f , NR e , PR e , P(O)R e , O, S, Se, C=O, C=S, C=Se, C=NR e , C=CR e R f , S=O, SO2, CR e R f , SiR e R f , and GeR e R f selected from the group consisting of; R e and R f can condense or combine to form a ring; each R a , R b , R c , and R d independently represents substitution from mono-substitution to the maximum allowable number, or no substitution; R a1 , R b1 , R c1 , R d1 , R e1 , R a , R b , R c , R d , R e , and R fEach of them is independently a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R a1 R b1 R c1 R d1 R a R b R c R d Any two substituents of and R are selected from the group consisting of (which can condense or bond to form a ring or form a polydentate ligand).

[0168] M(L A ) p (L B ) q (L C ) r In some embodiments of the compounds having the formula of, L B and L C are each independently

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0169] M(L A ) p (L B ) q (L C ) r In some embodiments of the compound having the formula, L A is selected from L Ai (wherein i is an integer from 1 to 335); L B is selected from L Bk (wherein k is an integer from 1 to 836), When the compound has the formula Ir(L Ai )3, the compound is selected from the group consisting of Ir(L A1 )3 to Ir(L A335 )3; When the compound has the formula Ir(L Ai )(L Bk )2, the compound is Ir(L A1 )(L B1 )2 to Ir(L A335 )(LB836 ) selected from the group consisting of 2; where the compound has the formula Ir(L Ai )2(L Bk ), the compound is selected from the group consisting of Ir(L A1 )2(L B1 ) to Ir(L A335 )2(L B836 ); where the compound has the formula Ir(L Ai )2(L Cj-I ), the compound is selected from the group consisting of Ir(L A1 )2(L C1-I ) to Ir(L A335 )2(L C1416-I ); where the compound has the formula Ir(L Ai )2(L Cj-II ), the compound is selected from the group consisting of Ir(L A1 )2(L C1-II ) to Ir(L A335 )2(L C1416-II ); each L Bk has the structure defined as follows:

Chemical formula

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[0170] RD1 ~R D246 is the structure defined in List 9 below:

Chem.

Chem.

Chem.

Chem.

[0171] The compounds of the present disclosure

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Chem.

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[0172] In some embodiments, the compound having the first ligand L of Formula I described herein A can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, the percent deuteration has its ordinary meaning and includes the percent of hydrogen atoms (e.g., positions that are hydrogen or deuterium) that can be replaced by deuterium atoms.

[0173] In some embodiments, ligand L A is the first emissive ligand of the compound. In some embodiments, ligand L B and / or L C is a co-ligand.

[0174] As used herein, a co-ligand is a ligand having a higher free ligand T1 energy. The free ligand T1 energy can be determined by computational procedures using density functional theory (DFT) modeling. For example, DFT calculations can be performed using LACVP *It can be carried out using the B3LYP functional in the basis set. In the first stage, the geometric structure of the complex is optimized while constraining the triplet spin density on each ligand. In the second stage, the geometric structure is re-optimized without imposing constraints. The spin density needs to remain localized on each respective ligand. The ligand where the spin density is localized in the lowest energy structure is regarded as the luminescent ligand. That ligand is regarded as the primary luminescent ligand when the energy difference from the second ligand is greater than 0.1 eV or 0.20 eV, or 0.30 eV.

[0175] Effective length of the ligand: In some embodiments of the first aspect, each of the first luminescent ligand and the auxiliary ligand has an effective length, and the effective length of the first luminescent ligand is at least 3 Å greater than the effective length of the second ligand.

[0176] In some embodiments, the ligand L of formula I A has a ligand axis defined as an axis passing through the bond between ring A and ring B of the ligand.

[0177] Furthermore, each ligand L A has a ligand center defined as the midpoint of the bond connecting ring A and ring B. Furthermore, each ligand has a ligand bisector defined as an infinite line passing through the metal to the ligand center.

[0178] Furthermore, each ligand L A has a length vector defined for each atom within the ligand. Each length vector connects the relevant atom to the ligand center. Furthermore, each ligand L A is L 1 and L 2 has values of, where L 1 is the highest value obtained among the products (magnitude of the length vector)×(cosine of the angle between the length vector and the ligand axis) on the ring A side of the ligand bisector, and L 2is the maximum value obtained among the products (magnitude of the length vector) × (cosine of the angle formed by the length vector and the ligand axis) on the ring B side of the ligand bisector line. In these calculations and subsequent calculations, including cases where parts can rotate around the axis, the measurements are made using the molecule in the conformational state with the lowest total energy given by the geometry optimization in the ground state, using the CEP-31G basis set and the DFT in the B3LYP functional.

[0179] The effective length of the ligand is the sum of its L 1 and L 2 measured as. Examples of each of these values are shown using the chemical structures in FIG. 4. The calculated values of L 1 and L 2 for the example of the iridium complex in FIG. 4 are shown in Table 1 below.

Table 2

[0180] The transition dipole moment (TDM) can be calculated by performing TD-DFT calculations using the B3LYP functional and the DYALL-V2Z_ZORA-J-PT-SEG basis set with the spin-orbit ZORA Hamiltonian.

[0181] In some embodiments, the first ligand has an effective length that is at least 5 Å greater than the second ligand. In some embodiments, the first ligand has an effective length that is at least 8 Å greater than the second ligand.

[0182] In some embodiments, the first ligand has at least 5 more non-hydrogen atoms than the second ligand. In some embodiments, the first ligand has at least 10 more non-hydrogen atoms than the second ligand. In some embodiments, the first ligand has at least 12 more non-hydrogen atoms than the second ligand.

[0183] In some embodiments, the first ligand has a molecular weight that is at least 100 amu greater than the molecular weight of the second ligand. In some embodiments, the first ligand has a molecular weight that is at least 150 amu greater than the molecular weight of the second ligand. In some embodiments, the first ligand has a molecular weight that is at least 200 amu greater than the molecular weight of the second ligand.

[0184] In some embodiments, the first ligand has at least three more aliphatic methylene carbons (e.g., CH2) than the second ligand. In some embodiments, the first ligand has at least five more aliphatic methylene carbons than the second ligand. In some embodiments, the first ligand has at least eight more aliphatic methylene carbons than the second ligand.

[0185] In some embodiments, the compound includes a tetradentate ligand formed from one of the first ligand and the second ligand, or from the first ligand bound to the second ligand. In some embodiments, the first ligand and the second ligand bind to form a tetradentate ligand.

[0186] In some embodiments, the difference in the number of R * moieties between the first ligand and the second ligand in the compound is at least two. In some embodiments of the first aspect, the difference in the number of R * moieties between the first ligand and the second ligand is at least three. In some embodiments of the first aspect, the difference in the number of R * moieties between the first ligand and the second ligand is at least four.

[0187] In some embodiments, the first ligand includes at least two more R * moieties in the compound than the second ligand. In some embodiments, the second ligand includes at least two more R * moieties than the first luminescent ligand.

[0188] As used herein, each R *The moiety is independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0189] In some embodiments, each R * moiety is independently selected from the group consisting of halogen, CF3, CN, F, C=O, and OR w wherein each R w is independently selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0190] In some embodiments, metal M has an atomic weight greater than 40. In some such embodiments, metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu. In some such embodiments, metal M is Ir or Pt. In some such embodiments, metal M is Pt.

[0191] In some embodiments, the metal complex compound further comprises a third ligand.

[0192] In some embodiments, the first ligand and the third ligand are the same. In some embodiments, the second ligand and the third ligand are the same.

[0193] In some embodiments, the first ligand and the third ligand are the same auxiliary ligand, and the second ligand is a luminescent ligand. In some embodiments, the first ligand and the third ligand are different auxiliary ligands, and the second ligand is a luminescent ligand. In some embodiments, the second ligand and the third ligand are the same luminescent ligand, and the first ligand is an auxiliary ligand.

[0194] In some embodiments of the second aspect, the second vector F2 forms an angle greater than 45 degrees with F1.

[0195] When multiple pairs of atoms meet the requirements of the first binding vector M1, the pair that forms the longest first binding vector meeting the other requirements is selected. When multiple pairs of atoms meet the requirements of the second binding vector M2, the pair that forms the longest second binding vector meeting the other requirements is selected.

[0196] In some embodiments, the complex compound has a first free vector F1 represented by a first binding vector M1 that connects any two atoms in the compound, passes within 1 Å of the metal, and has a length exceeding 18 Å; the compound has a second free vector F2 represented by a second binding vector M2 that connects any two atoms in the compound and has a length exceeding 18 Å; the angle between the luminescent transition dipole moment vector and the cross product of the vectors F1 and F2 is less than 45 degrees.

[0197] In some embodiments, the atoms forming the second binding vector M2 are within the same ligand, and the atoms forming the first binding vector M1 are within different ligands. In some embodiments, the atoms forming the second binding vector M2 are within a ligand different from any of the atoms forming the first binding vector M1.

[0198] In some embodiments, the second vector F2 forms an angle exceeding 45 degrees with F1.

[0199] In some embodiments of the second aspect, the second vector F2 is the longest vector that connects any two atoms within the molecule and forms an angle greater than 60 degrees with F1.

[0200] In some embodiments of the second aspect, the lengths of F1 and F2 are both greater than 20 Å. In some embodiments of the second aspect, the lengths of F1 and F2 are both greater than 22 Å.

[0201] In some embodiments, the angle between the luminescent transition dipole moment vector and the cross product of the vectors F1 and F2 is less than 30 degrees. In some embodiments, the angle between the luminescent transition dipole moment vector and the cross product of the vectors F1 and F2 is less than 20 degrees.

[0202] In some embodiments, the compound has a plane P defined by the free vectors F1 and F2 represented by the corresponding binding vectors M1 and M2, the plane P is parallel to M1 and M2 and passes through the metal M; the sum of the perpendicular distance from the plane P to the farthest atom above the plane P and the perpendicular distance from the plane P to the farthest atom below the plane P is less than 14 Å. In some such embodiments, the sum of the perpendicular distance from the plane P to the farthest atom above the plane P and the perpendicular distance from the plane P to the farthest atom below the plane P is less than 12 Å. In some such embodiments, the sum of the perpendicular distance from the plane P to the farthest atom above the plane P and the perpendicular distance from the plane P to the farthest atom below the plane P is less than 10 Å.

[0203] The perpendicular distance from the plane P is calculated using the standard formula for the distance of a point from a plane:

Equation

[0204] In some embodiments, the metal coordination complex compounds described herein can be at least 10% deuterated, at least 20% deuterated, at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, the percent deuteration has its ordinary meaning and includes the percent of hydrogen atoms (e.g., positions that are hydrogen or deuterium) that can be replaced by deuterium atoms.

[0205] C. OLEDs and Devices of the Present Disclosure In another aspect, the present disclosure also provides an OLED device comprising a first organic layer comprising a compound disclosed in the section of the compounds of the present disclosure.

[0206] In some embodiments, the OLED comprises an anode; a cathode; and an organic layer disposed between the anode and the cathode, the organic layer comprising a metal coordination complex compound described herein.

[0207] In some embodiments, the organic layer may be a light-emitting layer, and the compound described herein may be a light-emitting dopant or a non-light-emitting dopant.

[0208] In some embodiments, the organic layer is at least 10% deuterated. In some embodiments, at least one compound is at least 10% deuterated. In some embodiments, each compound in the organic layer is at least 10% deuterated.

[0209] In some embodiments, the organic layer is at least 50% deuterated. In some embodiments, at least one compound is at least 50% deuterated. In some embodiments, each compound in the organic layer is at least 50% deuterated.

[0210] In some embodiments, the organic layer is at least 90% deuterated. In some embodiments, at least one compound is at least 90% deuterated. In some embodiments, each compound in the organic layer is at least 90% deuterated.

[0211] In some embodiments, the organic layer may further include a host, the host includes a triphenylene-containing benzocondensed thiophene or benzocondensed furan, and any substituent in the host is C n H 2n+1 , OC n H 2n+1 , OAr1, N(C n H 2n+1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 , C≡CC n H 2n+1 , Ar1, Ar1-Ar2, C n H 2n -Ar1 is a non-condensed substituent independently selected from the group consisting of, or is unsubstituted, where n is an integer from 1 to 10; Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and their heteroaromatic analogs.

[0212] In some embodiments, the organic layer may further include a host, the host includes at least one chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, triazine, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

[0213] In some embodiments, the host is

Chemical formula

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Chemical formula

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Chemical formula

[0214] In some embodiments, the host may be selected from Host Group 2 consisting of:

Chemical Formula

Chemical Formula

[0215] In some embodiments, the organic layer may further include a host, and the host includes a metal complex.

[0216] In some embodiments, the compounds described herein may be sensitizers; the device may further include an acceptor; and the acceptor may be selected from the group consisting of fluorescent emitters, delayed fluorescent emitters, and combinations thereof.

[0217] In yet another aspect, the OLEDs of the present disclosure may also include a light-emitting region that includes the compounds disclosed in the section on the compounds of the present disclosure.

[0218] In some embodiments, the light-emitting region may include a metal coordination complex compound described herein.

[0219] In some embodiments, at least one of the anode, the cathode, or a new layer disposed on the organic light-emitting layer functions as an enhancement layer. The enhancement layer includes a plasmonic material that non-radiatively couples to the emitter material and exhibits surface plasmon resonance that transfers excited state energy from the emitter material to surface plasmon polaritons in a non-radiative mode. The enhancement layer is provided within a threshold distance from the organic light-emitting layer, and 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 at the threshold distance, the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further includes an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the enhancement layer on the opposite side of the organic light-emitting layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the enhancement layer of the light-emitting layer but still outcouples energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered into free space as photons. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device, including but not limited to organic waveguide modes, substrate modes, or other waveguide modes. When the energy is scattered into a non-free space mode of the OLED, other outcoupling schemes may be incorporated to extract the energy into free space. In some embodiments, one or more intervening layers may be disposed between the enhancement layer and the outcoupling layer. Examples of the intervening layer may be a dielectric material including organic, inorganic, perovskite, oxides, and may include laminates and / or mixtures of these materials.

[0220] The enhancement layer changes the effective properties of the medium in which the emitter material is present, resulting in any or all of a decrease in luminous efficiency, a change in the 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 a reduction in the efficiency roll-off of the OLED device. When the enhancement layer is disposed on the cathode side, the anode side, or both sides, an OLED device that utilizes any of the above effects can be obtained. In addition to the specific functional layers shown in the various OLED examples described and illustrated herein, the OLEDs according to the present disclosure may include any of the other functional layers often seen in OLEDs.

[0221] The enhancement layer may be composed of a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material 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 laminates of these materials. Generally, a metamaterial is a medium composed of different materials, and as a whole medium, it functions differently from the sum of its material parts. In particular, an optically active metamaterial is defined as a material having both a negative dielectric constant and a negative magnetic permeability. On the other hand, a hyperbolic metamaterial is an anisotropic medium in which the dielectric constant or magnetic permeability has different signs 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 propagation direction on the length scale of the wavelength of light. Using terms that can be understood by those skilled in the art, the dielectric constant of the metamaterial in the propagation direction can be described using the effective medium approximation. Plasmonic materials and metamaterials provide ways to control the propagation of light, which can enhance OLED performance in many ways.

[0222] In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features arranged periodically, quasi-periodically, or randomly. In some embodiments, the wavelength-sized features and the sub-wavelength-sized features have sharp edges.

[0223] In some embodiments, the outcoupling layer has wavelength-sized features arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features 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 on a material. In these embodiments, the outcoupling layer can be adjusted by at least one of changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, or adding an additional layer on the plurality of nanoparticles, changing the thickness of the enhancement layer, and / or changing the material of the enhancement layer. The plurality of nanoparticles of the device can be formed from at least one of a metal, a dielectric material, a semiconductor material, an alloy of a metal, a mixture of dielectric materials, a laminate or layer of one or more materials, and / or a core of a certain type of material coated with a shell of another type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles, and 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 laminates of these materials. The plurality of nanoparticles may have additional layers disposed thereon. In some embodiments, the polarization of the emission can be adjusted using the outcoupling layer. By varying the dimensionality and periodicity of the outcoupling layer, the type of polarization that is preferentially outcoupled to air can be selected. In some embodiments, the outcoupling layer also functions as an electrode of the device.

[0224] 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 can include a compound disclosed in the section of the above compounds of the present disclosure.

[0225] In some embodiments, the consumer product includes an anode; a cathode; and an organic light emitting diode (OLED) having an organic layer disposed between the anode and the cathode, the organic layer may include a metal coordination complex compound described herein.

[0226] In some embodiments, the consumer product is one of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, an indoor or outdoor lighting and / or signaling light, a head-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cellular phone, a tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay (display less than 2 inches diagonal), a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall including multiple displays arranged side by side, a theater or stadium screen, a phototherapy device, and a signboard.

[0227] Generally, an OLED includes 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 move respectively towards the oppositely charged electrodes. When an electron and a hole localize on the same molecule, an "exciton", a localized electron-hole pair having an excited energy state, is formed. Light is emitted via a photoelectron emission mechanism when the exciton relaxes. In some instances, the exciton may localize as an excimer or an exciplex. Non-radiative mechanisms such as thermal relaxation may occur, but are generally considered undesirable.

[0228] Some OLED materials and configurations are described in U.S. Patent Nos. 5,844,363, 6,303,238, and 5,707,745, which are hereby incorporated by reference in their entirety.

[0229] Initial OLEDs used luminescent molecules that emit light ( "fluoresce") from their singlet state, as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated herein by reference in its entirety. Fluorescent emission generally occurs within a time frame of less than 10 nanoseconds.

[0230] More recently, OLEDs having luminescent materials that emit light from the triplet state ( "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 herein by reference in their entirety. Phosphorescence is described in more detail in paragraphs 5 - 6 of U.S. Patent No. 7,279,704, which is incorporated herein by reference.

[0231] FIG. 1 shows an organic light-emitting device 100. The figure is not necessarily drawn to scale. Device 100 can include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, a light-emitting layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by sequentially depositing the described layers. The properties and functions of these various layers, as well as examples of materials, are described in more detail in paragraphs 6 - 10 of U.S. Patent No. 7,279,704, which is incorporated herein by reference.

[0232] For each of these layers, further examples are available. For example, the flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is one 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 herein by reference in its entirety. Examples of light-emitting materials and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is one doped with Li at a molar ratio of 1:1 as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entireties, disclose examples of cathodes including a composite cathode having a thin layer of a metal such as Mg:Ag having a transparent, conductive, sputter-deposited ITO layer thereon. The theory and use of blocking layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated herein by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. A description of the protective layer can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0233] Figure 2 shows the inverted OLED 200. The device includes a substrate 210, a cathode 215, a light-emitting layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by depositing the described layers in sequence. The most common OLED configuration has a cathode disposed on top of the anode, and since the device 200 has a cathode 215 disposed under the anode 230, the device 200 can be referred to as an “inverted” OLED. Materials similar to those described for the device 100 may be used in the corresponding layers of the device 200. Figure 2 provides an example of how some layers can be omitted from the structure of the device 100.

[0234] The simple layer structures illustrated in FIGS. 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the present disclosure can be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs can be realized by combining the various layers described in various ways, or the layers can be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Many of the examples provided herein describe the various layers as including a single material, but it is understood that combinations of materials such as mixtures of hosts and dopants, or more generally mixtures, may be used. Also, the layers may have various sub-layers. The names given to the various layers herein are not intended to be strictly limiting. For example, in the device 200, the hole transport layer 225 transports holes and injects holes into the light-emitting layer 220 and can be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED can be described as having an “organic layer” disposed between the cathode and the anode. This organic layer can include a single layer or can further include multiple layers of different organic materials such as those described with respect to FIGS. 1 and 2.

[0235] Structures and materials not specifically described may be used, such as OLEDs (PLEDs) composed of a polymer material such as that disclosed in Friend et al., U.S. Patent No. 5,247,190, which is incorporated by reference in its entirety. As a further example, an OLED having a single organic layer may be used. The OLEDs may be stacked, for example, as described in Forrest et al., U.S. Patent No. 5,707,745, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layer structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface for improving outcoupling, such as a mesa structure described in Forrest et al., U.S. Patent No. 6,091,195, which is incorporated by reference in its entirety, and / or a recessed structure described in Bulovic et al., U.S. Patent No. 5,834,893, which is incorporated by reference in its entirety.

[0236] Unless otherwise specified, any of the layers of the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation such as those described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated herein by reference in their entirety; inkjet; organic vapor deposition (OVPD) such as those described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated herein by reference in its entirety; and organic vapor jet printing (also referred to as OVJP, organic vapor jet deposition (OVJD)) such as those described in U.S. Pat. No. 7,431,968, which is incorporated herein by reference in its entirety. Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include masking such as those described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated herein by reference in their entirety; deposition via cold welding; and patterning associated with some of the deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods may be used. The materials to be deposited can be modified to be compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, which can be branched or unbranched and preferably contain at least 3 carbons, can be used in small molecules to enhance the ability to undergo solution processing. Substituents having 20 or more carbons can be used, with 3 to 20 carbons being a preferred range. Materials having an asymmetric structure can have better solution processability than those having a symmetric structure, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents can be used to enhance the ability of small molecules to undergo solution processing.

[0237] Devices fabricated in accordance with embodiments of the present disclosure may optionally further include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in an environment containing moisture, vapor, and / or gas, etc. The barrier layer may be deposited on the substrate, above, below, or adjacent to the electrodes, or on any other part of the device including the edges. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds or both. Preferred barrier layers include mixtures of polymeric and non-polymeric materials as described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are hereby incorporated by reference in their entirety. For the mixture to be considered a "mixture", the polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and / or simultaneously. The weight ratio of the polymeric material to the non-polymeric material can range from 95:5 to 5:95. The polymeric and non-polymeric materials may be made from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

[0238] 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 various electrical products or intermediate components. Examples of such electrical products or intermediate components include display screens, lighting devices, such as discrete light source devices or lighting panels, etc., that can be utilized by end-user product manufacturers. Such electronic component modules can optionally include drive electronics and / or power supplies. Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products having one or more incorporated electronic component modules (or units). Consumer products including OLEDs containing the compounds of the present disclosure in the organic layers of the OLEDs are disclosed. Such consumer products include any type of product including one or more light sources and / or one or more certain types of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, bulletin boards, indoor or outdoor lighting and / or signal sending lights, head-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays arranged side by side, theater or stadium screens, light therapy devices, and billboards. The devices fabricated in accordance with the present disclosure can be controlled using a variety of control mechanisms, including passive matrix and active matrix. Many of the devices are intended for use within a temperature range comfortable for humans, such as from 18°C to 30°C, more preferably room temperature (20 - 25°C), although they can also be used outside of this temperature range, for example, from -40°C to +80°C Celsius.

[0239] Further details regarding OLEDs, and the above definitions, can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0240] 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 utilize the materials and structures. More generally, organic devices such as organic transistors may utilize the materials and structures.

[0241] In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further includes a layer comprising carbon nanotubes.

[0242] In some embodiments, the OLED further includes a layer comprising a delayed fluorescence emitter. In some embodiments, the OLED includes an RGB pixel array or a white and color filter pixel array. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal less than 10 inches or an area less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of 50 square inches. In some embodiments, the OLED is an illumination panel.

[0243] In some embodiments, the compound can be a luminescent dopant. In some embodiments, the compound can generate luminescence via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. Application No. 15 / 700,352, which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or a combination of these processes. In some embodiments, the luminescent 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 the others). If there are multiple ligands coordinated to the metal, in some embodiments, all of the ligands can be the same. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, all of the ligands can be different from each other. This also applies to embodiments where the ligands coordinated to the metal can be linked to other ligands coordinated to that metal to form tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, if the coordinating ligands are linked together, in some embodiments, all of the ligands can be the same, and in some other embodiments, at least one of the linked ligands can be different from the other ligands.

[0244] In some embodiments, the compound can be used as a phosphorescence sensitizer in an OLED in which one or more layers in the OLED contain 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 phosphorescence sensitizer, this compound must be capable of energy transfer to the acceptor, and the acceptor will either emit energy or further transfer the energy to the final emitter. The concentration of the acceptor can range from 0.001% to 100%. The acceptor can be present in either the same layer as the phosphorescence 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 originate from any or all of the sensitizer, acceptor, and final emitter.

[0245] According to another aspect, a formulation comprising the compounds described herein is also disclosed.

[0246] The OLEDs disclosed herein can be incorporated into one or more of consumer products, electronic component modules, and lighting panels. In some embodiments, the organic layer can be a light-emitting layer, the compound can be a luminescent dopant, while in other embodiments, the compound can be a non-luminescent dopant.

[0247] In yet another aspect of the present disclosure, a formulation comprising the novel compounds disclosed herein is described. The formulation can include one or more components selected from the group consisting of solvents, hosts, hole injection materials, hole transport materials, electron blocking materials, hole blocking materials, and electron transport materials disclosed herein.

[0248] The present disclosure encompasses any chemical structure that includes the novel compounds of the present disclosure, or monovalent or polyvalent variants thereof. In other words, the compounds of the present invention, or monovalent or polyvalent variants thereof, can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of monomers, polymers, macromolecules, and supramolecules (also known as giant molecules). As used herein, "monovalent variant of a compound" refers to a portion 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, "polyvalent variant of a compound" refers to a portion that is identical to the compound except that two or more hydrogens have been removed and replaced with bonds to the rest of the chemical structure. In the example of a supramolecule, the compounds of the present invention can also be incorporated into the supramolecular complex without covalent bonds.

[0249] D. Combinations of Compounds of the Present Disclosure with Other Materials The materials described herein as useful in a particular layer in an organic light-emitting device can be used in combination with a wide variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in combination 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 can be useful in combination with the compounds disclosed herein, and one of ordinary skill in the art can readily refer to the literature to identify other materials that can be useful in combination.

[0250] a) Conductive (Conductivity) Dopants: The charge transport layer is doped with a conductive dopant, which greatly changes the density of charge carriers and thereby its conductivity. Conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductive dopant, and an n-type conductive dopant is used in the electron transport layer.

[0251] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below together with the references that disclose these materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.

Chemical formula

[0252] b) HIL / HTL: The hole injection / transport materials used in the present invention are not particularly limited, and any compound that is usually used as a hole injection / transport material may be used. Examples of the materials include phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorohydrocarbons; polymers having a conductive dopant; conductive polymers such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; metal oxide derivatives such as MoO x and the like; p-type semiconductor organic compounds such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile; metal complexes, and crosslinkable compounds, but are not limited thereto.

[0253] Examples of the aromatic amine derivatives used for HIL or HTL include, but are not limited to, the following general structures.

Chemical formula

[0254] Ar 1 ~Ar 9Each of which consists of a group of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, 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 a group of the same or different types of groups selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and are directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic cyclic group, and are selected from a group consisting of 2 to 10 cyclic structural units bonded to each other. Each Ar may be unsubstituted or 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 acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0255] In one aspect, Ar 1 ~Ar9 independently, [Chem.] (wherein k is an integer from 1 to 20; X 101 ~X 108 is C (including C(CH)) or N; Z 101 is NAr 1 , O, or S; Ar 1 has the same group defined above) and is selected from the group consisting of.

[0256] Examples of metal complexes used in HIL or HTL include the following general formula: [Chem.] (wherein Met is a metal that can have an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, and Y 101 and Y 102 are independently selected from C, N, O, P, and S; L 101 is a co-ligand; k' is an integer value from 1 to the maximum number of ligands that can bind to the metal; and k'+k'' is the maximum number of ligands that can bind to the metal), but are not limited thereto.

[0257] In one embodiment, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. In another embodiment, (Y 101 -Y 102 ) is a carbene ligand. In another embodiment, Met is selected from Ir, Pt, Os, and Zn. In a further embodiment, the metal complex has a minimum oxidation potential of less than about 0.6 V in solution with respect to the Fc + / Fc couple.

[0258] Non-limiting examples of HIL materials and HTL materials that can be used in OLEDs in combination with the materials disclosed in this specification are provided in the references that disclose these materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, US06517957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872,Illustrated below together with WO2014030921, WO2014034791, WO2014104514, WO2014157018. [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

[0259] c) EBL: The electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons emitted from the light emitting layer. The presence of such a blocking layer in the device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking the blocking layer. Also, the blocking layer can be used to limit light emission to a desired region of the 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 the EBL contains the same molecule or the same functional group as that used as one of the hosts described below.

[0260] d) Host: The light emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as a light emitting material and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound can be used as long as the triplet energy of the host is greater than that of the dopant. Any host material can be used with any dopant as long as the triplet criterion is satisfied.

[0261] Examples of metal complexes used as hosts are of the following general formula: [Chemical formula] (wherein Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, and Y 103 and Y 104 are independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can bind to the metal; and k'+k'' is the maximum number of ligands that can bind to the metal) are preferred.

[0262] In one aspect, the metal complex is [Chemical formula] (wherein (O-N) is a bidentate ligand having a metal coordinated to atoms O and N).

[0263] In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y 103 -Y 104 ) is a carbene ligand.

[0264] In one aspect, the host compound comprises at least one 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; 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 at least one selected from the group consisting of 2 to 10 cyclic structural units of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, which are directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic cyclic group, bonded to each other. Each option within each group may be unsubstituted or 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 acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0265] In one aspect, the host compound has the following groups in the molecule: [Chemical formula] (wherein R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when this is aryl or heteroaryl, it has the same definition as Ar above. k is an integer from 0 to 20 or from 1 to 20. X 101 ~X 108 are independently selected from C (including CH) or N. Z 101 and Z 102 are independently selected from NR 101 , O, or S.) and includes at least one of them.

[0266] Non-limiting examples of host materials that can be used in OLEDs in combination with the materials disclosed in this specification are illustrated below together with the 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, US7154114, 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, US9466803.

Chem.

Chem.

[0267] e) Additional emitters: One or more additional emitter dopants may be used in combination with the compounds of the present disclosure. Examples of additional emitter dopants are not particularly limited, and any compound may be used as long as it is a compound usually used as an emitter material. Examples of suitable emitter materials include, but are not limited to, compounds that can emit light through phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also called E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes. Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed in this specification, 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, US06699599, US06916554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559,US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, US6303238, US6413656, US6653654, US6670645, US6687266, US6835469, US6921915, US7279704, US7332232, US7378162, US7534505, US7675228, US7728137, US7740957, US7759489, US7951947, US8067099, US8592586, US8871361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450 are exemplified below.

Chemical formula

Chemical formula

Chemical formula

[0268] f) HBL: The hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons emitted from the light emitting layer. The presence of such a blocking layer in the device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking the blocking layer. Also, the blocking layer can be used to limit light emission to a desired region of the OLED. In some embodiments, the HBL material has a lower HOMO (farther 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 (farther from the vacuum level) and / or higher triplet energy than one or more of the hosts closest to the HBL interface.

[0269] In one aspect, the compound used for the HBL contains the same molecule or the same functional group as that used as the host described above.

[0270] In another aspect, the compound used for the HBL has the following group in the molecule [Chemistry] (where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3) and includes at least one of them.

[0271] g) ETL: The electron transport layer (ETL) can include a material capable of transporting electrons. The electron transport layer can be intrinsic (undoped) or can be doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound can be used as long as it is normally used for transporting electrons.

[0272] In one aspect, the compound used in the ETL has the following groups in the molecule:

Chem.

[0273] In another aspect, the metal complex used in the ETL has the following general formula:

Chem.

[0274] Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed in this specification are exemplified below together with the 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, US6656612, US8415031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535.

Chemical formula

Chemical formula

Chemical formula

[0275] h) Charge Generation Layer (CGL) In tandem or stacked OLEDs, the CGL plays an important role in performance and consists of an n-doped layer and a p-doped layer for electron and hole injection, respectively. Electrons and holes are supplied from the CGL and the electrodes. The consumed electrons and holes in the CGL are replenished by the electrons and holes injected from the cathode and anode, respectively, and then the bipolar current gradually reaches a stable state. Typical CGL materials include n-type and p-type conductive dopants used in the transport layer.

[0276] In any of the above compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. The minimum amount of hydrogen in the deuterated compound is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. Thus, without limitation, any specifically listed substituents such as methyl, phenyl, pyridyl, etc. may be in their non-deuterated, partially deuterated, and fully deuterated versions. Similarly, classes of substituents such as alkyl, aryl, cycloalkyl, heteroaryl, etc., without limitation thereto, may be in their non-deuterated, partially deuterated, and fully deuterated versions.

[0277] It is understood that the various embodiments described herein are merely by way of example and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the invention. Thus, the invention as claimed can include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It is understood that the various theories as to why the invention works are not intended to be limiting.

[0278] E. Experimental Data To measure the VDR, a film for angular-dependent photoluminescence was fabricated by vacuum thermal evaporation of an arbitrary layer of 50 Å of H2 on a glass substrate pretreated with UV-ozone, followed by vacuum thermal evaporation of 400 Å of H1 or H3 doped with 3 - 5% of the emitter. Next, the polarization angle-dependent photoluminescence was measured using a Fluxim Phelos system with an excitation source of 340 nm or 405 nm and adapted to Setfos software to obtain the VDR. The Phelos spectral intensity versus angle is obtained by integrating the wavelength region over the range excluding the scattering of the excitation source.

[0279] The fitting routine within Setfos is as follows. The optical stack is set up identically to the experiment using a 0.7 mm glass substrate for measuring luminescence, a 40 nm EML film with an emitter, and finally air. The emitter distribution is located above the air-EML interface and is set as an exponential function with a width of 50 nm. The integrated p-polarized and s-polarized spectral intensity versus angle are used as the input targets for the Setfos fitting / optimization routine. The optimization fitting parameters are the emitter orientation (VDR), the luminescence intensity, and the EML refractive index. The VDR obtained from this fitting is the reported value as VDR = vertical dipole ratio (0.33 is random, and any value less than 0.33 is aligned horizontally net).

Table 3

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0280] These experimental VDR results in Table 6 are representative of the criteria claimed herein to achieve a VDR complex exceeding 0.33 as compared to the comparative examples (CE) listed in the table.

[0281] Synthesis Example

[0282] Synthesis of 5-fluoro-2-(m-tolyl)pyridine: [Chemical formula] 2-Chloro-5-fluoropyridine (3.90 g, 3.000 mL, 1 equivalent, 29.7 mmol), m-tolylboronic acid (6.05 g, 1.5 equivalents, 44.5 mmol), Pd(PPh3)4 (1.71 g, 0.05 equivalent, 1.48 mmol), and potassium carbonate (8.20 g, 2 equivalents, 59.3 mmol) were combined in dioxane (75.00 mL) and water (25.00 mL) and heated to reflux for 16 hours. The mixture was diluted with water and brine and extracted with EtOAc. After drying and concentration under vacuum, the mixture was purified by column chromatography to obtain the product as a colorless oil, 5.15 g (93%).

[0283] Synthesis of 5-neopentyl-1-phenyl-1H-pyrazole: [Chemical formula] 5-Iodo-1-phenyl-1H-pyrazole (5.000 g, 1 equiv, 18.51 mmol), S-Phos (608.0 mg, 0.08 equiv, 1.481 mmol), and Pd2(dba)3 were combined in THF (50.00 mL) under nitrogen, and a solution of neopentylzinc(II) bromide in THF (6.010 g, 55.54 mL, 0.500 M, 1.5 equiv, 27.77 mmol) was added. The pale yellow solution was refluxed for 16 h and quenched with water and brine. It was extracted with EtOAc, then dried, purified by column chromatography, and further triturated in heptane to give the product as a white solid, yield 1.77 g (45%).

[0284] Synthesis of 4-bromo-5-neopentyl-1-phenyl-1H-pyrazole:

Chemical formula

[0285] Synthesis of 5-neopentyl-1,4-diphenyl-1H-pyrazole:

Chemical formula

[0286] Synthesis of iridium dimer:

Chemical formula

[0287] Synthesis of iridium solvent triflate:

Chemical formula

[0288] Synthesis of E31:

Chemical formula

Claims

1. A metal coordination complex compound capable of functioning as an emitter in an organic light emitting device (OLED) at room temperature; The metal coordination complex compound comprises a first emissive ligand coordinated to a metal; said metal coordination complex compound having a vertical dipole ratio (VDR) greater than 0.33; At least one of the following is true: (1) the first emissive ligand has a spin density population greater than 60%; (2) the first emissive ligand has a natural transition orbital (NTO) particle population greater than 50%; (3) the first emissive ligand has a ligand-centered character (LC) of greater than 30%; (4) the first emitting ligand has a complex inter-ligand charge transfer (LLCT) of less than 40%; (5) A metal coordination complex compound, wherein the first emissive ligand has an M / T ratio greater than 0.

42.

2. the metal coordination complex compound further comprises a second ligand coordinated to the metal; and / or the first emissive ligand and the second ligand each have an effective length, the effective length of the first emissive ligand being at least 3 Å greater than the effective length of the second ligand; and / or the first emissive ligand has at least 5 more non-hydrogen atoms than the second ligand; and / or the first emissive ligand has a molecular weight at least 100 amu greater than the molecular weight of the second ligand; and / or 2. The metal coordination complex compound of claim 1, wherein said first emissive ligand has at least three more aliphatic methylene carbons than said second ligand.

3. the metal coordination complex compound further comprises a second ligand coordinated to the metal; The metal coordination complex compound has a constraint vector M that connects any two atoms in the metal coordination complex compound and passes within 2 Å of the metal. １ A first free vector F １ and the constraint vector M １ is greater than 18 Å in length; The metal coordination complex compound has a binding vector M ２ A second free vector F ２ having The constraint vector M ２ is greater than 18 Å in length; The metal coordination complex compound has a transition dipole moment vector, and the transition dipole moment vector and vector F １ and F ２ 2. The metal coordination complex compound of claim 1 , wherein the angle between the cross product of

4. the metal coordination complex compound further comprises a second ligand coordinated to the metal; The metal coordination complex compound has two metal donor bonds in a trans configuration; The metal coordination complex compound has a first vector W formed between any atom around the metal coordination complex compound and the metal. １ having The metal coordination complex compound has a second vector W formed between the metal and any other atom around the metal coordination complex compound. ２ having W １ and W ２ each of the magnitudes is greater than 9.5 Å; and The metal coordination complex compound has a luminescent transition dipole moment vector, and the luminescent transition dipole moment vector and vector W １ and W ２ 2. The metal coordination complex compound of claim 1 , wherein the angle between the cross product of

5. M (L Ａ ) ｐ (L Ｂ ) ｑ (L Ｃ ) ｒ (wherein L Ｂ and L Ｃ are each a bidentate ligand; 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.

6. Ligand L Ａ but, 【Chemistry 1】 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 (In the formula, X １ ~X １９ are each independently C or N; Each R Ａ and R Ｂ independently represent one substitution up to the maximum possible number of substitutions, or no substitution; Each R Ａ , R Ｂ , R ｅ , and R ｆ is independently hydrogen or a substituent selected from the group consisting of General Substituents defined herein; Y １ , Y ２ , and Y ３ Each of the groups independently represents BR ｅ , N.R. ｅ , P.R. ｅ , O, S, Se, C=O, S=O, SO ２ , C.R. ｅ R ｆ , SiR ｅ R ｆ , and GeR ｅ R ｆ selected from the group consisting of:

6. The metal coordination complex compound of claim 5, wherein any two of the substituents are selected from the group consisting of:

7. L Ｂ and L Ｃ However, each independently, 【Chemistry 9】 【Chemistry 10】 (In the formula, T is selected from the group consisting of B, Al, Ga, and In; K １’ is a single bond, O, S, NR ｅ , P.R. ｅ , B.R. ｅ , C.R. ｅ R ｆ , and SiR ｅ R ｆ selected from the group consisting of: Y １ ~Y １３ each is independently selected from the group consisting of C and N; Y' is BR ｅ , B.R. ｅ R ｆ , N.R. ｅ , P.R. ｅ , P(O)R ｅ , O, S, Se, C=O, C=S, C=Se, C=NR ｅ , C=CR ｅ R ｆ , S=O, SO ２ , C.R. ｅ R ｆ , SiR ｅ R ｆ , and GeR ｅ R ｆ selected from the group consisting of: R ｅ and R ｆ can be fused or linked to form a ring; Each R ａ , R ｂ , R ｃ , and R ｄ independently represent one substitution up to the maximum permitted number of substitutions, or no substitution; R ａ１ , R ｂ１ , R ｃ１ , R ｄ１ , R ｅ１ , R ａ , R ｂ , R ｃ , R ｄ , R ｅ , and R ｆ each is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R ａ１ , R ｂ１ , R ｃ１ , R ｄ１ , R ａ , R ｂ , R ｃ , and R ｄ any two of the substituents may be fused or linked to form a ring or to form a multidentate ligand.

8. L Ａ L Ａｉ wherein i is an integer from 1 to 335; Ｂ L Ｂｋ where k is an integer from 1 to 836; The metal coordination complex compound is represented by the formula Ir(L Ａｉ ) ３ When the metal coordination complex compound has the formula: Ａ１ ) ３ ~Ir(L Ａ３３５ ) ３ selected from the group consisting of: The metal coordination complex compound is represented by the formula Ir(L Ａｉ ) (L Ｂｋ ) ２ When the metal coordination complex compound has the formula: Ａ１ ) (L Ｂ１ ) ２ ~Ir(L Ａ３３５ ) (L Ｂ８３６ ) ２ selected from the group consisting of: The metal coordination complex compound is represented by the formula Ir(L Ａｉ ) ２ (L Ｂｋ ), the metal coordination complex compound has Ir(L Ａ１ ) ２ (L Ｂ１ ) to Ir(L Ａ３３５ ) ２ (L Ｂ８３６ ) selected from the group consisting of; The metal coordination complex compound is represented by the formula Ir(L Ａｉ ) ２ (L Ｃｊ－Ｉ ), the metal coordination complex compound has Ir(L Ａ１ ) ２ (L Ｃ１－Ｉ ) to Ir(L Ａ３３５ ) ２ (L Ｃ１４１６－Ｉ ) selected from the group consisting of; The metal coordination complex compound is represented by the formula Ir(L Ａｉ ) ２ (L Ｃｊ－ＩＩ ), the metal coordination complex compound has Ir(L Ａ１ ) ２ (L Ｃ１－ＩＩ ) to Ir(L Ａ３３５ ) ２ (L Ｃ１４１６－ＩＩ ) selected from the group consisting of; In the formula, each L Ｂｋ is a structure defined as follows: 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 【Chemistry 18】 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemical 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【Chemistry 27】 【Chemistry 28】 【Chemical 29】 【Chemistry 30】 【Chemistry 31】 【Chemistry 32】 【Chemical 33】 【Chemical 34】 【Chemistry 35】 【Chemical 36】 【Chemical 37】 【Chemical Formula 38】 【Chemical 39】 where j is an integer from 1 to 1416, and each L Ｃｊ－Ｉ is the formula 【Chemistry 40】 each L Ｃｊ－ＩＩ is the formula 【Chemistry 41】 and L Ｃｊ－Ｉ and L Ｃｊ－ＩＩ Each L in Ｃｊ About R ２０１ and R ２０２ are each independently the following list 8: 【Chemistry 42】 【Chemistry 43】 【Chemistry 44】 【Chemistry 45】 【Chemistry 46】 【Chemistry 47】 【Chemistry 48】 【Chemistry 49】 【Chemistry 50】 is defined as Ｄ１ ~R Ｄ２４６ is the structure defined in Listing 9 below: 【Chemistry 51】 【Chemistry 52】 【Chemistry 53】 The metal coordination complex compound of claim 5 , having the formula:

9. anode; A cathode; and an organic light emitting device comprising an organic layer disposed between the anode and the cathode, the organic layer comprising a metal coordination complex compound capable of functioning as a light emitter in the organic light emitting device at room temperature; The metal coordination complex compound comprises a first emissive ligand coordinated to a metal; said metal coordination complex compound having a vertical dipole ratio (VDR) greater than 0.33; At least one of the following is true: (1) the first emissive ligand has a spin density population greater than 60%; (2) the first emissive ligand has a natural transition orbital (NTO) particle population greater than 50%; (3) the first emissive ligand has a ligand-centered character (LC) of greater than 30%; (4) the first emitting ligand has a complex inter-ligand charge transfer (LLCT) of less than 40%; (5) An organic light-emitting device, wherein the first emissive ligand has an M / T ratio greater than 0.

42.

10. anode; A cathode; and a consumer product comprising an organic light emitting device comprising an organic layer disposed between the anode and the cathode, the organic layer comprising a metal coordination complex compound capable of functioning as a light emitter in the organic light emitting device at room temperature; The metal coordination complex compound comprises a first emissive ligand coordinated to a metal; said metal coordination complex compound having a vertical dipole ratio (VDR) greater than 0.33; At least one of the following is true: (1) the first emissive ligand has a spin density population greater than 60%; (2) the first emissive ligand has a natural transition orbital (NTO) particle population greater than 50%; (3) the first emissive ligand has a ligand-centered character (LC) of greater than 30%; (4) the first emitting ligand has a complex inter-ligand charge transfer (LLCT) of less than 40%; (5) the first emissive ligand has an M / T ratio greater than 0.42; The consumer product is one of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for indoor or outdoor illumination and / or signaling, a head-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a mobile phone, a tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall including multiple displays aligned together, a theater or stadium screen, a light therapy device, and a signage.

Images