Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. The present disclosure provides a metal complex compound. The metal complex compound is capable of acting as an emitter in an organic light emitting device (OLED) at room temperature, and has a vertical dipole ratio (VDR) greater than 0.33 in the OLED. Formulations, OLEDs, and consumer products including the metal complex compounds are also provided.

Description

Technical Field

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

[0002] For various reasons, optoelectronic devices that utilize organic materials have become increasingly popular. Many of the materials used to fabricate such devices are relatively inexpensive, so organic optoelectronic devices have the potential for a cost advantage over inorganic devices. Additionally, the inherent properties of organic materials, such as their flexibility, can make them more suitable for certain 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 an organic thin film that emits light when a voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for applications such as flat panel displays, lighting, and backlighting.

[0004] One application of phosphorescent emissive molecules is full-color displays. Industry standards for such displays require pixels that are suitable for emitting specific colors (referred to as "saturated" colors). Specifically, these standards require saturated red, green, and blue pixels. Alternatively, an OLED can be designed to emit white light. In conventional liquid crystal displays, absorption filters are used to filter the emission from a white backlight to produce red, green, and blue emissions. The same technique can also be used for OLEDs. A white OLED can be a single emission layer (EML) device or a stacked structure. Color can be measured using CIE coordinates well known in the art. Summary of the Invention

[0005] In some OLED applications, a novel metal coordination complex compound is disclosed that is capable of acting as an emitter in an organic light emitting device (OLED) at room temperature. The compound includes a first emissive ligand coordinated to the metal;

[0006] The vertical dipole ratio (VDR) of the compound > 0.33; and

[0007] At least one of the following is true:

[0008] (1) The spin density population of the emissive ligand > 60%;

[0009] (2) The natural transition orbital (NTO) population of the emissive ligand > 50%;

[0010] (3) The ligand-centered character (LC) of the emissive ligand > 30%;

[0011] (4) The ligand-to-ligand charge transfer (LLCT) of the emissive ligand < 40%; and

[0012] (5) The M / T ratio of the emissive ligand > 0.42.

[0013] In another aspect, the present disclosure provides a formulation comprising a metal coordination complex compound as described herein.

[0014] In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a metal coordination complex compound as described herein.

[0015] In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a metal coordination complex compound as described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 An organic light-emitting device is shown.

[0017] Figure 2 An inverted organic light-emitting device without a separate electron transport layer is shown.

[0018] Figure 3 A graph of modeled P-polarized photoluminescence versus angle for emitters having different vertical dipole ratio (VDR) values is shown.

[0019] Figure 4 The structure of a metal coordination complex compound as described herein and its related measurements and characteristics are shown.

[0020] Figure 5 The structure of a metal coordination complex compound as described herein and the positions of the related free and bound vectors defining plane P are shown. DETAILED DESCRIPTION

[0021] A. Terms

[0022] Unless otherwise specified, the following terms used herein are defined as follows:

[0023] As used herein, the term "organic" includes polymeric materials and small molecule organic materials that can be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and a "small molecule" can actually be quite large. In some cases, small molecules can include repeating units. For example, the use of a long-chain alkyl group as a substituent does not remove a molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, such as as pendant groups on the polymer backbone or as part of the backbone. Small molecules can also serve as the core portion of a dendrimer, which consists of a series of chemical shells built on the core portion. The core portion of a dendrimer can be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be "small molecules", and all dendrimers currently used in the OLED field are considered to be small molecules.

[0024] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as "disposed over" a second layer, the first layer is disposed further from the substrate. There can be other layers between the first and second layers unless it is specified that the first layer "contacts" the second layer. For example, even though there are various organic layers between the cathode and the anode, the cathode can still be described as "disposed over" the anode.

[0025] As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in a liquid medium in the form of a solution or suspension and / or deposited from a liquid medium.

[0026] When a ligand is considered to directly contribute to the photosensitive properties of an emissive material, the ligand can be referred to as "photosensitive". When a ligand is not considered to contribute to the photosensitive properties of an emissive material, the ligand can be referred to as "auxiliary", but an auxiliary ligand can modify the properties of a photosensitive ligand.

[0027] As used herein, and as would be generally understood by one of ordinary skill in the art, if the first energy level is closer to the vacuum energy level, then the first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy level is "greater than" or "higher than" the second HOMO or LUMO energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum energy level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (a less negative EA). On a conventional energy level diagram with the vacuum energy level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A "higher" HOMO or LUMO energy level appears closer to the top of this diagram than a "lower" HOMO or LUMO energy level.

[0028] As used herein, and as would be generally understood by one of ordinary skill in the art, if the first work function has a higher absolute value, then the first work function is "greater than" or "higher than" the second work function. Since the work function is typically measured as a negative number relative to the vacuum energy level, this means that a "higher" work function is more negative. On a conventional energy level diagram with the vacuum energy level at the top, a "higher" work function is illustrated as being farther from the vacuum energy level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow different rules than the work function.

[0029] The terms "halo", "halogen", and "halo group" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0030] The term "acyl" refers to a substituted carbonyl (C(O)-R s ).

[0031] The term "ester" refers to a substituted oxycarbonyl (-O-C(O)-R s or -C(O)-O-R s ) group.

[0032] The term "ether" refers to an -OR s group.

[0033] The terms "thio" or "thioether" are used interchangeably and refer to an -SR s group.

[0034] The term "selenoalkyl" refers to a -SeR s group.

[0035] The term "sulfinyl" refers to -S(O)-R s group.

[0036] The term "sulfonyl" refers to -SO2-R s group.

[0037] The term "phosphino" refers to -P(R s )2 group, where each R s can be the same or different.

[0038] The term "silyl" refers to -Si(R s )3 group, where each R s can be the same or different.

[0039] The term "germyl" refers to -Ge(R s )3 group, where each R s can be the same or different.

[0040] The term "boryl" refers to -B(R s )2 group or its Lewis adduct -B(R s )3 group, where R s can be the same or different.

[0041] In each of the above, R s can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0042] The term "alkyl" refers to and includes straight-chain and branched-chain alkyls. Preferred alkyls are alkyls containing one to fifteen carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, etc. Additionally, the alkyl can be optionally substituted.

[0043] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyls. Preferred cycloalkyls are cycloalkyls containing 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. Additionally, the cycloalkyl can be optionally substituted.

[0044] The term "heteroalkyl" or "heterocycloalkyl" refers respectively to an alkyl or cycloalkyl group having at least one carbon atom replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Additionally, the heteroalkyl or heterocycloalkyl may optionally be substituted.

[0045] The term "alkenyl" means and includes straight-chain and branched alkenyl groups. An alkenyl group is essentially an alkyl group that includes at least one carbon-carbon double bond in the alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group that includes at least one carbon-carbon double bond in the cycloalkyl ring. The term "heteroalkenyl" as used herein refers to an alkenyl group in which at least one carbon atom is replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group may optionally be substituted.

[0046] The term "alkynyl" means and includes straight-chain and branched alkynyl groups. An alkynyl group is essentially an alkyl group that includes at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may optionally be substituted.

[0047] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted by an aryl group. Additionally, the aralkyl may optionally be substituted.

[0048] The term "heterocyclic group" means and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Aromatic heterocyclic groups may be used interchangeably with heteroaryl groups. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom, and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl, etc., and cyclic ethers / sulfides such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. Additionally, the heterocyclic group may be optionally substituted.

[0049] The term "aryl" means and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. The polycycle may have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), where at least one of the rings is an aromatic hydrocarbon group, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six, ten, or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, fluoranthene, phenanthrene, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. Additionally, the aryl may optionally be substituted.

[0050] The term "heteroaryl" means and includes monocyclic aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many instances, O, S, or N are preferred heteroatoms. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have one to six heteroatoms. The hetero polycyclic system may have two or more rings where two atoms are shared by two adjacent rings (the rings are "fused"), where at least one of the rings is a heteroaryl, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. The hetero polycyclic aromatic ring system may have one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryls are heteroaryls containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryls 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, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborole, 1,3-azaborole, 1,4-azaborole, borazon, and their nitrogen analogs. Additionally, the heteroaryl may optionally be substituted.

[0051] Among the aryls and heteroaryls listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and their respective nitrogen analogs are of particular interest.

[0052] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl are independently unsubstituted or independently substituted with one or more common substituents.

[0053] In many cases, the general substituents are selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenyl, sulfinyl, sulfonyl, phosphino and combinations thereof.

[0054] In some cases, the preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio and combinations thereof.

[0055] In some cases, the more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, thio and combinations thereof.

[0056] In other cases, the most preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof.

[0057] The terms "substituted" and "substitution" mean that a substituent other than H is bonded to the relevant position, such as carbon or nitrogen. For example, when R 1 represents monosubstitution, one R 1 must not be H (i.e., substitution). Similarly, when R 1 represents disubstitution, two R 1 must not be H. Similarly, when R 1 represents zero or no substitution, R 1 can be, for example, hydrogen at the available valences of the ring atoms, such as the carbon atoms of benzene and the nitrogen atom in pyrrole, or simply represents none for ring atoms with fully saturated valences, such as the nitrogen atom in pyridine. The maximum possible number of substitutions in the ring structure will depend on the total number of available valences in the ring atoms.

[0058] As used herein, "in combination" means that one or more members of an applicable list are combined to form a known or chemically stable arrangement that can be envisioned by one of ordinary skill in the art from the applicable list. For example, an alkyl group and deuterium can be combined to form a partially or fully deuterated alkyl group; a halogen and an alkyl group can be combined to form a haloalkyl substituent; and a halogen, an alkyl group, and an aryl group can be combined to form a haloarylalkyl group. In one example, the term substituted includes combinations of two to four of the listed groups. In another example, the term substituted includes combinations of two to three groups. In yet another example, the term substituted includes combinations of two groups. Preferred combinations of substituents are combinations that contain up to fifty atoms that are not hydrogen or deuterium, or combinations that include up to forty atoms that are not hydrogen or deuterium, or combinations that include up to thirty atoms that are not hydrogen or deuterium. In many instances, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0059] As used herein, the "aza" designation in fragments such as aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C-H groups in the corresponding aromatic ring can be replaced by a nitrogen atom. For example, and without any limitation, aza-triphenylene encompasses dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be covered by the terms as set forth herein.

[0060] 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, Patent Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. US2011 / 0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference to Ming Yan et al., Tetrahedron 2015, 71, 1425 - 30 and Atzrodt et al., Angew. Chem. Int. Ed. (Review) 2007, 46, 7744 - 65 (which are incorporated by reference in their entirety) describe effective routes for the deuteration of methylene hydrogens in benzylamines and for the replacement of aromatic ring hydrogens with deuterium, respectively.

[0061] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name can be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were the entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attached fragments are considered equivalent.

[0062] In some cases, a pair of adjacent substituents may optionally be joined or fused to form a ring. Preferred rings are five-, six- or seven-membered carbocyclic or heterocyclic rings, including cases where a part of the ring formed by the pair of substituents is saturated and cases where a part of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that the two substituents involved can be adjacent to each other on the same ring, or on two adjacent rings having the two closest available substitutable positions (such as the 2,2'-positions in biphenyl or the 1,8-positions in naphthalene), as long as they can form a stable fused ring system.

[0063] B. Compounds of the present disclosure

[0064] In some OLED applications, a novel metal coordination complex compound is disclosed, which is capable of acting as an emitter in an organic light-emitting device (OLED) at room temperature. The compound comprises a first emissive ligand coordinated to the metal;

[0065] The vertical dipole ratio (VDR) of the compound > 0.33; and

[0066] At least one of the following conditions is true:

[0067] (1) The spin density population of the first emissive ligand > 60%;

[0068] (2) The natural transition orbital (NTO) population of the first emissive ligand > 50%;

[0069] (3) The ligand-centered character (LC) of the first emissive ligand > 30%;

[0070] (4) The ligand-ligand charge transfer (LLCT) of the first emissive ligand < 40%; and

[0071] (5) The M / T ratio of the first emissive ligand > 0.42.

[0072] Although the minimum requirement is that at least one of the above five conditions in the compound is true, any number of combinations of the five conditions can be true.

[0073] As used herein, room temperature is defined as approximately 22 °C (e.g., 22 °C ± 1 °C).

[0074] As used herein, "spin density" refers to the electron density applied to free radicals and other open-shell structures. It is defined as the total electron density of one spin electron minus the total electron density of the other spin electrons.

[0075] Density functional theory (DFT) was used to calculate the triplet spin density of the compound. Calculations were performed using the unrestricted B3LYP functional and the CEP-31G basis set. The first triplet excited state was geometrically optimized in vacuo by setting the spin multiplicity to three. Subsequently, the spin density was calculated as the difference between the α and β spin densities using the CubeGen utility in the Gaussian program. All calculations were carried out using the Gaussian program. To determine the spin density populations on each atom and each group of atoms, Löwdin population analysis was performed as described by P.-O. Löwdin ( P.-O.). J. Chem. Phys. 1950, 18, 365 and P.-O. Löwdin. Adv. Quantum Chem. 1970, 5, 185. This was achieved by partitioning the spin density into atom-centered fractions that together constitute the molecule. These fractions were then collected individually or in groups as required.

[0076] DFT calculations were performed to determine the energy of the lowest triplet excited state (T1) of the compound, the percentage of ligand-centered (LC) character, and the percentage of ligand–ligand charge transfer (LLCT) involved in T1. Data were collected using the program Gaussian16. The B3LYP functional and the CEP-31G basis set were used to optimize the geometries. The excited state energies were calculated at the optimized ground state geometries by TDDFT. The THF solvent was simulated using the self-consistent reaction field to further improve the agreement with experiments. The LC character and LLCT fractions were determined by analysis of the transition density matrix of the excited states.

[0077] The calculated values obtained using the DFT functional sets and basis sets identified above are theoretical values. Computational composite protocols, such as Gaussian16 using the B3LYP and CEP-31G protocols as used herein, rely on the assumption that electronic effects are additive and can thus be extrapolated to the complete basis set (CBS) limit using larger basis sets. However, when the research goal is to understand the variations in HOMO, LUMO, S1, T1, bond dissociation energies, etc. of a series of structurally related compounds, additive effects are expected to be similar. Thus, although the absolute error using B3LYP may be more significant compared to other computational methods, 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, e.g., Hong et al., Chem. Mater. 2016, 28, 5791-98, 5792-93 and the Supplementary Information (discussing the reliability of DFT calculation results in the case of OLED materials). In addition, regarding iridium or platinum complexes that can be used in the OLED field, the data obtained from DFT calculations are closely related to actual experimental data. See Tavasli et al., J. Mater. Chem. 2012, 22, 6419-29, 6422 (Table 3) (showing DFT calculations closely related to actual data for various emissive complexes); Morello, G.R., J. Mol. Model. 2017, 23:174 (studying various DFT functional sets and basis sets and inferring that the combination of B3LYP and CEP-31G is particularly accurate for emissive complexes). The determination of the excited state transition characteristics is performed as a post-processing step of the DFT and TDDFT calculations mentioned above. This analysis allows the excited state to be decomposed into a hole (i.e., the position where the excitation starts) and an electron (i.e., the final position of the excited state). In addition, since this analysis is performed on the properties of the calculation, 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).

[0078] Natural transition orbitals (NTOs) are obtained by singular value decomposition of the transition density matrix in the Gaussian16 program. The transition density matrix is obtained by TDDFT at the ground state geometry, which is optimized using the B3LYP functional and the CEP-31G basis set. The THF solvent is simulated using the self-consistent reaction field. Hole NTOs are the orbitals obtained by unitary transformation of the regular occupied molecular orbitals. Particle NTOs are the orbitals obtained by unitary transformation of the regular virtual molecular orbitals and represent the positions of the excited electrons. The NTO hole / particle populations of atoms and each grouping of atoms are obtained by Löwdin population analysis.

[0079] 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 at the maximum peak wavelength (λ max ) ± 15 nm, and T is the total area (normalized intensity) of the spectrum between the points where the spectral intensity is 0.1%. A high M / T ratio means that the dopant has a narrow line shape (i.e., a larger portion 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 OLED emission region onto a quartz substrate. The emission spectrum of the thin film is measured using a Hamamatsu Quantaurus-QY Plus UV-NIR absolute PL quantum yield spectrometer with an excitation wavelength of 340 nm.

[0080] The vertical dipole ratio (VDR) is the overall average fraction of dipoles oriented perpendicular to the substrate plane in the sample (where the vertical line and the normal of the substrate are the same). A similar concept is the horizontal dipole ratio (HDR), which is the overall average fraction of dipoles oriented horizontally with respect to the substrate plane. By definition, VDR + HDR = 1. The VDR can be measured by angle-dependent, polarization-dependent photoluminescence measurements. By comparing the measured emission pattern as a function of polarization of the photoexcited thin film test sample with a computer-modeled pattern, the VDR of the emission layer can be determined. For example, Figure 3 shows the modeled data of p-polarized emission. The modeled p-polarized angular photoluminescence (PL) of emitters with different VDRs is plotted. A modeled PL peak is observed in the p-polarized PL near 45 degrees, where the peak PL is larger when the VDR of the emitter is higher.

[0081] In the use of generating Figure 3In this example, there is a 30 nm thick material film 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 respect to the photoluminescence intensity 1 (at zero degrees perpendicular to the film surface). As the VDR of the emitter changes, the peak near 45 degrees increases significantly. When using software to fit the VDR of experimental data, the modeled VDR will change until the difference between the modeled data and the experimental data is minimized.

[0082] Importantly, the VDR represents the average dipole orientation of the luminescent compound. Thus, if there are additional emitters in the emission layer that do not contribute to the emission, then the VDR measurement will not report or reflect their VDR. Additionally, by including a host that interacts with the emitter, the VDR of a given emitter can be changed, resulting in a measured VDR of the layer that is different from the VDR of the emitter in a different host. Further, in some embodiments, it is necessary to form an exciplex or excimer in the emissive state between two adjacent molecules. These emissive states can have a VDR that is different from the VDR when only one component emits in the exciplex or excimer or when it is present in the sample.

[0083] The emitter emits in a direction perpendicular to its transition dipole moment (TDM) vector because this aligns with the electric field vector of the resulting light wave. Thus, in a conventional OLED, it is desirable for the emitter TDM vectors to be highly horizontally aligned to obtain light that emits towards an observer in a direction perpendicular to the substrate. Doing so maximizes the out-coupling of light and minimizes efficiency loss mechanisms such as optical waveguide or plasmon coupling within the OLED or the substrate. Plasmon coupling is typically a major limiting factor in OLED efficiency, and in the art, plasmon coupling is designed by spacing the emitter from the cathode, thereby compromising the device voltage.

[0084] For the reasons described above, vertically aligned emitters, i.e., those with a high VDR, have not been widely studied or applied in the field of OLEDs simply because it contradicts the good design purpose of conventional OLED devices. It is now found that for a well-designed plasmonic OLED, a high degree of plasmon coupling is desirable. Thus, in this case, high-VDR emitters can be used to increase the rate or yield of plasmon coupling and improve the efficiency of plasmonic OLEDs.

[0085] In some embodiments, the OLED is a plasmonic OLED. In some embodiments, the OLED is a waveguide OLED.

[0086] In some embodiments, the VDR of the compound is equal to or greater than 0.35. In some embodiments, the VDR of the compound is equal to or greater than 0.4. In some embodiments, the VDR of the compound is equal to or greater than 0.45. In some embodiments, the VDR of the compound is equal to or greater than 0.5. In some embodiments, the VDR of the compound is equal to or greater than 0.6. In some embodiments, the VDR of the compound is equal to or greater than 0.7. In some embodiments, the VDR of the compound is equal to or greater than 0.8. In some embodiments, the VDR of the compound is equal to or greater than 0.9.

[0087] In some embodiments of the metal coordination complex compounds of the present disclosure, at least two of the above-listed conditions (1) to (5) are true. In some embodiments, at least three of conditions (1) to (5) are true. In some embodiments, at least four of conditions (1) to (5) are true.

[0088] In some embodiments, the spin density population of the first emissive ligand > 60%. In some embodiments, the spin density population of the first emissive ligand > 70%. In some embodiments, the spin density population of the first emissive ligand > 80%. In some embodiments, the spin density population of the first emissive ligand > 90%. In some embodiments, the spin density population of the first emissive ligand > 95%.

[0089] In some embodiments, the NTO particle population of the first emissive ligand > 50%. In some embodiments, the NTO particle population of the first emissive ligand > 60%. In some embodiments, the NTO particle population of the first emissive ligand > 70%. In some embodiments, the NTO particle population of the first emissive ligand > 80%. In some embodiments, the NTO particle population of the first emissive ligand > 90%.

[0090] In some embodiments, the LC of the first emissive ligand > 30%. In some embodiments, the LC of the first emissive ligand > 40%. In some embodiments, the LC of the first emissive ligand > 50%. In some embodiments, the LC of the first emissive ligand > 60%. In some embodiments, the LC of the first emissive ligand > 70%. In some embodiments, the LC of the first emissive ligand > 80%. In some embodiments, the LC of the first emissive ligand > 90%.

[0091] In some embodiments, the complex LLCT of the first emissive ligand < 40%. In some embodiments, the complex LLCT of the first emissive ligand < 30%. In some embodiments, the complex LLCT of the first emissive ligand < 20%. In some embodiments, the complex LLCT of the first emissive ligand < 10%.

[0092] In some embodiments, the M / T ratio of the first emissive ligand > 0.42. In some embodiments, the M / T ratio of the first emissive ligand > 0.44. In some embodiments, the M / T ratio of the first emissive ligand > 0.46. In some embodiments, the M / T ratio of the first emissive ligand > 0.48. In some embodiments, the M / T ratio of the first emissive ligand > 0.50.

[0093] In some embodiments, the first emissive ligand comprises a polycyclic fused-ring system coordinated to a metal.

[0094] 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 nitrogenous 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 nitrogenous variant contains exactly one N atom at the 6-position (ortho to O, S, or Se), while containing a substituent at the 7-position (meta to O, S, or Se).

[0095] 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.

[0096] In some of these embodiments, the polycyclic fused-ring structure comprises at least five fused rings. In some embodiments, the polycyclic fused-ring structure comprises four 6-membered rings and one 5-membered ring or three 6-membered rings and two 5-membered rings. In some embodiments containing two 5-membered rings, the 5-membered rings are fused together. In some embodiments containing two 5-membered rings, the 5-membered rings are separated by at least one 6-membered ring. In some embodiments having one 5-membered ring, the 5-membered ring is fused to the ring coordinated to Ir, the second 6-membered ring is fused to the 5-membered ring, the third 6-membered ring is fused to the second 6-membered ring, and the fourth 6-membered ring is fused to the third 6-membered ring.

[0097] In some of these embodiments, the polycyclic fused-ring structure comprises an aza-form of the fused rings as described above. In some such embodiments, the polycyclic fused-ring structure contains exactly one aza N atom. In some such embodiments, the polycyclic fused-ring structure contains exactly two aza N atoms, which may be in one ring or in two different rings. In some such embodiments, the ring having the aza N atom is separated from the Ir atom by at least two additional rings. In some such embodiments, the ring having the aza N atom is separated from the Ir atom by at least three additional rings. In some such embodiments, each ortho position of the aza N atom is substituted.

[0098] In some embodiments, the compound further comprises a second ligand coordinated to the metal; and / or wherein each of the emissive ligand and the second ligand has an effective length, and wherein the effective length of the emissive ligand is at least and / or

[0099] wherein the emissive ligand has at least 5 more non-hydrogen atoms than the second ligand; and / or

[0100] wherein the molecular weight of the emissive ligand is at least 100 amu greater than the molecular weight of the second ligand; and / or

[0101] wherein the emissive ligand has at least 3 more aliphatic methylene carbons than the second ligand.

[0102] In some embodiments, the compound further comprises a second ligand coordinated to the metal; wherein the compound has a first free vector F1, which is represented by a bound vector M1 that connects any two atoms in the compound and passes within the of the metal, and the length of the bound vector M1 is greater than wherein the compound has a second free vector F2, which is represented by a bound vector M2 that connects any two atoms in the compound; wherein the length of the bound vector M2 is greater than and wherein 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.

[0103] Figure 5 showing the compound Examples. As defined herein, a vector defined by two points in space in the reference frame of a compound is referred to as a "bound vector" (e.g., M1 and M2). The position of the bound vector in space in the reference frame of the compound is fixed at the specific position within the reference frame of the compound. In contrast, a "free vector" such as F1 or F2 only has magnitude and direction. In this case, the plane P is defined by the free vectors F1 and F2 and the metal M. Thus, the cross product of F1 and F2 will define the normal of the plane P.

[0104] Regarding Figure 5 Sample calculations for the compounds in are provided in Table 2 below:

[0105]

[0106] In this regard, the coordinates of the atoms are determined using the lowest energy structure in the triplet state, where spin is restricted on the emitting ligand, using DFT in the LACVP* basis set and B3LYP functional. The transition dipole moment (TDM) is then calculated using this geometry.

[0107] In Table 2, "maximum ┴ distance from plane P " means the maximum perpendicular distance of the atom from plane P.

[0108] In some embodiments, the second free vector F2 forms an angle greater than 45 degrees with the first free vector F1.

[0109] In cases where more than one pair of atoms meets the requirements for the first bound vector M1, the pair that forms the longest first bound vector meeting the other requirements is selected. In cases where more than one pair of atoms meets the requirements for the second bound vector M2, the pair that forms the longest second bound vector meeting the other requirements is selected.

[0110] In some embodiments, the complex compound has a first free vector F1, which is represented by a first bound vector M1 that connects any two atoms in the compound and passes within the and has a length greater than ; wherein the compound has a second free vector F2, which is represented by a second bound vector M2 that connects any two atoms in the compound and has a length greater than ; and wherein the angle between the emission transition dipole moment vector and the cross product of the vectors F1 and F2 is less than 45 degrees.

[0111] In some embodiments, the atoms forming the second bound vector M2 are in the same ligand, and the atoms forming the first bound vector M1 are in different ligands. In some embodiments, the atoms forming the second bound vector M2 are in a ligand different from any of the atoms forming the first bound vector M1.

[0112] In some embodiments, the second vector F2 forms an angle greater than 45 degrees with F1.

[0113] In some embodiments of the second aspect, the second vector F2 is the longest vector connecting any two atoms in the molecule and forming an angle greater than 60 degrees with F1.

[0114] In some embodiments of the second aspect, the lengths of both F1 and F2 are greater than In some embodiments of the second aspect, the lengths of both F1 and F2 are greater than

[0115] In some embodiments, the angle between the emission 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 emission transition dipole moment vector and the cross product of the vectors F1 and F2 is less than 20 degrees.

[0116] In some embodiments, the compound has a plane P defined by free vectors F1 and F2, the free vectors being represented by corresponding bound vectors M1 and M2, and the plane P is parallel to M1 and M2 and passes through the metal M; and the sum of the perpendicular distances 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 In some such embodiments, the sum of the perpendicular distances 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 In some such embodiments, the sum of the perpendicular distances 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

[0117] The perpendicular distance from the plane P is calculated using the standard formula for the distance of a point from a plane:

[0118]

[0119] where a, b, c are the components of the plane normal vector, x0, y0, z0 are the coordinates of the atom, and d is the constant of the plane equation ensuring that the plane passes through the metal atom.

[0120] In some embodiments, the compound comprises a first ligand and a second ligand each coordinated to the metal. In some embodiments of such compounds, the compound may have two metal coordination bonds in a trans configuration; wherein the compound has a first vector W1 formed between any atom on the outer periphery of the compound and the metal; wherein the compound has a second vector W2 formed between any other atom on the outer periphery of the compound and the metal; wherein each magnitude of W1 and W2 is greater than and wherein the compound has an emission transition dipole moment vector, and the angle between the emission transition dipole moment vector and the cross product of the vectors W1 and W2 is less than 45 degrees.

[0121] In some embodiments, the compound has a transition dipole moment vector, and the compound is tetracoordinate square planar, wherein the deviation of the transition dipole moment vector from a reference plane defined by at least three atoms of the ligand periphery that are at least apart from each other is not less than 45 degrees.

[0122] In some embodiments, the metal M is selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu.

[0123] In some embodiments, the compound has the formula M(L A ) p (L B ) q (L C ) r , where L A is an emissive ligand; L B and L C are each bidentate ligands; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p + q + r is the oxidation state of the metal M.

[0124] In embodiments where the compound has the formula M(L A ) p (L B ) q (L C ) r , the compound can have a formula selected from the group consisting of Ir(L A )3, Ir(L A )(L B )2, Ir(L A )2(L B ), Ir(L A )2(L C ), and Ir(L A )(L B )(L C ); and wherein L A , L B , and L C are different from each other.

[0125] In embodiments where the compound has the formula M(L A ) p (L B ) q (L C ) rIn some embodiments, where L A Comprises the structure of formula I:

[0126]

[0127] Wherein moieties A and B are each independently a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5 - to 10 - membered carbocyclic or heterocyclic ring;

[0128] Wherein Z 1 -Z 4 Are each independently C or N;

[0129] Wherein K 1 And K 2 Are each independently selected from the group consisting of: 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 );

[0130] Wherein 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';

[0131] Wherein R A And R B Each independently represents mono - substitution to the maximum allowable substitution or no substitution;

[0132] Wherein each R, R', R α , R β , R A And R B Are independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof;

[0133] Wherein L A Coordinates with metal M;

[0134] Wherein M coordinates with at least one auxiliary ligand;

[0135] Wherein L Amay bind to one or more additional ligands to form a tridentate, tetradentate, pentadentate or hexadentate ligand; and

[0136] Any two substituents may bind or fuse to form a ring.

[0137] In some embodiments of Formula I, at least one of moieties A or B has a fused ring system comprising four or more 5- and / or 6-membered carbocyclic or heterocyclic rings.

[0138] In some embodiments of Formula I, each of R, R', Rα, Rβ, RA and RB is independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio and combinations thereof.

[0139] In some embodiments of Formula I, ligand L A has the structure of Formula I. In some embodiments, ligand L A has a structure consisting essentially of the structure of Formula I.

[0140] In some embodiments of Formula I, moieties A and B in Formula I are each independently a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- or 6-membered carbocyclic or heterocyclic ring. In some embodiments, each of moiety A and moiety B is independently aryl or heteroaryl.

[0141] 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 partially or fully deuterated. In some embodiments, at least one R B is partially or fully deuterated. In some embodiments, at least one of R or R' is partially or fully deuterated.

[0142] In some embodiments of Formula I, each of moiety A and moiety B is independently selected from the group consisting of moieties from 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.

[0143] In some embodiments of Formula I, the aza-variant includes one N located on a benzo ring. In some embodiments, the aza-variant includes one N located on a benzo ring and the N is bonded to metal M.

[0144] In some embodiments of Formula I, moiety A is monocyclic.

[0145] 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.

[0146] In some embodiments of Formula I, moiety A is pyridine, pyrazole, imidazole, or 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.

[0147] In some embodiments of Formula I, moiety A is a polycyclic fused ring containing three 5- or 6-membered carbon or heterocyclic rings. In some embodiments, moiety A is quinoline, isoquinoline, indazole, benzimidazole, or benzimidazole-derived carbene. In some embodiments, moiety A is a polycyclic fused ring containing at least four 5- or 6-membered carbon or heterocyclic rings.

[0148] In some embodiments of Formula I, moiety A comprises moiety A1 cyclized by moiety A2, wherein moiety A1 comprises Z 1 and each of moiety A1 and moiety A2 is independently selected from the group consisting of moieties in the list of cyclic moieties.

[0149] 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.

[0150] In some embodiments of Formula I, moiety A2 is benzene or naphthalene.

[0151] In some embodiments of Formula I, moiety B is monocyclic. 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.

[0152] 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.

[0153] In some embodiments of Formula I, moiety B is a polycyclic fused ring containing three 5- or 6-membered carbon or heterocyclic rings.

[0154] In some embodiments of Formula I, moiety B is carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthrene, anthracene, phenanthridine, and fluorene.

[0155] In some embodiments of Formula I, moiety B is a polycyclic fused ring containing at least four 5- or 6-membered carbon or heterocyclic rings.

[0156] In some embodiments of Formula I, moiety B comprises moiety B1 cyclized by moiety B2, wherein moiety B1 comprises Z 2 and each of moiety B1 and moiety B2 is independently selected from the group consisting of moieties in the list of cyclic moieties.

[0157] 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.

[0158] In some embodiments of Formula I, moiety B2 is benzene or naphthalene. In some embodiments, moiety B2 is dibenzofuran or naphthalene.

[0159] 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.

[0160] In some embodiments of Formula I, each of Z 2 to Z 4 is C. In some embodiments, at least one of Z 2 to Z 4 is N.

[0161] 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, exactly one of K 1 or K 2 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.

[0162] 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 ).

[0163] 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.

[0164] 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 ).

[0165] In some embodiments of a compound having a first ligand L A of Formula I, the ligand L A comprises an electron-withdrawing group selected from the group consisting of the structures in 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 , a substituted or unsubstituted dibenzoborole, a 1-substituted carbazole, a 1,9-substituted carbazole, a substituted or unsubstituted carbazole, a substituted or unsubstituted pyridine, a substituted or unsubstituted pyrimidine, a substituted or unsubstituted pyrazine, a substituted or unsubstituted pyridoxine, a substituted or unsubstituted triazine, a substituted or unsubstituted oxazole, a substituted or unsubstituted benzoxazole, a substituted or unsubstituted thiazole, a substituted or unsubstituted benzothiazole, a substituted or unsubstituted imidazole, a substituted or unsubstituted benzimidazole, a ketone, a carboxylic acid, an ester, a nitrile, an isonitrile, a sulfinyl group, a sulfonyl group, a partially and fully fluorinated alkyl group, a partially and fully fluorinated aryl group, a partially and fully fluorinated heteroaryl group, an alkyl group containing a cyano group, an aryl group containing a cyano group, a heteroaryl group containing a cyano group, an isocyanate,

[0166]

[0167] Where each R k1 represents mono-substitution to the maximum allowable substitution or no substitution;

[0168] Where Y G is selected from the group consisting of: BR e 、NR e 、PR e 、O, S, Se, C═O, S═O, SO2, CR e R f 、SiR e R f and GeR e R f' ; and

[0169] Where R k1 、R k2 、R k3 、R e and R f each independently is hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, selenyl, sulfinyl, sulfonyl, phosphino and combinations thereof.

[0170] In some embodiments of the compound of formula I having L A , the ligand L A comprises an electron-withdrawing group selected from the group consisting of the structures in the following EWG2 list:

[0171]

[0172]

[0173] In some embodiments of the compound of formula I having L A , the ligand L A comprises an electron-withdrawing group selected from the group consisting of the structures in the following EWG3 list:

[0174]

[0175] In some embodiments of the compound of formula I having L A , the ligand L AComprising an electron-withdrawing group selected from the group consisting of the structures in the following EWG4 list:

[0176]

[0177] In some embodiments of the compound having formula I of L A the ligand L A comprises an electron-withdrawing group, and the electron-withdrawing group is a π-deficient electron-withdrawing group. In some embodiments, the π-deficient electron-withdrawing group is selected from the group consisting of the structures in 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 dibenzoborolene, 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, aryl containing a cyano group, heteroaryl containing a cyano group, isocyanate,

[0178]

[0179] wherein the variables are the same as those defined previously.

[0180] In some embodiments of the compound having formula I of L A at least one of R, R', R α , R β , R A and R B is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one of R, R', R α , R β , RA and R B at least one of is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, R, R', R α , R β , R A and R B at least one of is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, R, R', R α , R β , R A and R B at least one of is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, R, R', R α , R β , R A and R B at least one of is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0181] In some embodiments of the compound having formula I A of L, at least one of R A is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one of R A is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one of R A is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one of R A is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one of R A is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0182] In some embodiments of the compound having formula I A of L, at least one of R B is or comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one of R B is or comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one of R B is or comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one of R B is or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one of R BAt least one of them is or contains an electron-withdrawing group from the Pi-EWG list as defined herein.

[0183] In some embodiments of the compound having formula I of L A R is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, R is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, R is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, R is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, R is or contains an electron-withdrawing group from the Pi-EWG list as defined herein.

[0184] In some embodiments of the compound having formula I of L A R' is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, R' is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, R' is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, R' is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, R' is or contains an electron-withdrawing group from the Pi-EWG list as defined herein.

[0185] In some embodiments of the compound having formula I of L A R α is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, R α is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, R α is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, R α is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, R α is or contains an electron-withdrawing group from the Pi-EWG list as defined herein.

[0186] In some embodiments of the compound having formula I of L A R β is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, R β is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, R β is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, R βis or comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, R β is or comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0187] In some embodiments of the compound of formula I of L A , at least one R A or R B comprises an electron-withdrawing group that is not F.

[0188] In some embodiments of the compound of formula I of L A , at least one R A comprises an electron-withdrawing group that is not F.

[0189] In some embodiments of the compound of formula I of L A , at least one R B comprises an electron-withdrawing group that is not F.

[0190] In some embodiments of the compound of formula I of L A , a total of at least two of R A and R B independently comprise an electron-withdrawing group that is not F.

[0191] In some embodiments of the compound of formula I of L A , at least one R A is or comprises an electron-withdrawing group other than F selected from the EWG1 list as defined herein. 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.

[0192] In some embodiments of the compound of formula I of L A , at least one R A is or comprises an electron-withdrawing group other than F selected from the EWG2 list as defined herein. In some embodiments, R A is an electron-withdrawing group other than F selected from the EWG2 list as defined herein. In some embodiments, R A comprises an electron-withdrawing group other than F selected from the EWG2 list as defined herein.

[0193] In some embodiments of the compound of formula I of L A , at least one R A is or comprises an electron-withdrawing group other than F selected from the EWG3 list as defined herein. In some embodiments, RA is an electron-withdrawing group other than F selected from the EWG3 list as defined herein. In some embodiments, R A comprises an electron-withdrawing group other than F selected from the EWG3 list as defined herein.

[0194] In some embodiments of the compound of formula I having L A at least one R A is or comprises an electron-withdrawing group other than F selected from the EWG4 list as defined herein. In some embodiments, R A is an electron-withdrawing group other than F selected from the EWG4 list as defined herein. In some embodiments, R A comprises an electron-withdrawing group other than F selected from the EWG4 list as defined herein.

[0195] In some embodiments of the compound of formula I having L A at least one R A is or comprises an electron-withdrawing group other than F selected from the Pi-EWG list as defined herein. In some embodiments, R A is an electron-withdrawing group other than F selected from the Pi-EWG list as defined herein. In some embodiments, R A comprises an electron-withdrawing group other than F selected from the Pi-EWG list as defined herein.

[0196] In some embodiments of the compound of formula I having L A at least one R B is or comprises an electron-withdrawing group other than F selected from the EWG1 list as defined herein. In some embodiments, R B is an electron-withdrawing group other than F selected from the EWG1 list as defined herein. In some embodiments, R B comprises an electron-withdrawing group other than F selected from the EWG1 list as defined herein.

[0197] In some embodiments of the compound of formula I having L A at least one R B is or comprises an electron-withdrawing group other than F selected from the EWG2 list as defined herein. In some embodiments, R B is an electron-withdrawing group other than F selected from the EWG2 list as defined herein. In some embodiments, R B comprises an electron-withdrawing group other than F selected from the EWG2 list as defined herein.

[0198] In some embodiments of the compound of formula I having L A at least one RB is or comprises an electron-withdrawing group other than F selected from the EWG3 list as defined herein. In some embodiments, R B is an electron-withdrawing group other than F selected from the EWG3 list as defined herein. In some embodiments, R B comprises an electron-withdrawing group other than F selected from the EWG3 list as defined herein.

[0199] In some embodiments of the compound of formula I having L A , at least one R B is or comprises an electron-withdrawing group other than F selected from the EWG4 list as defined herein. In some embodiments, R B is an electron-withdrawing group other than F selected from the EWG4 list as defined herein. In some embodiments, R B comprises an electron-withdrawing group other than F selected from the EWG4 list as defined herein.

[0200] In some embodiments of the compound of formula I having L A , at least one R B is or comprises an electron-withdrawing group other than F selected from the Pi-EWG list as defined herein. In some embodiments, R B is an electron-withdrawing group other than F selected from the Pi-EWG list as defined herein. In some embodiments, R B comprises an electron-withdrawing group other than F selected from the Pi-EWG list as defined herein.

[0201] In some embodiments of the compound having formula M(L A ) p (L B ) q (L C ) r , the ligand L B comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, L B comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, L B comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, L B comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, L B comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0202] In some embodiments of the compound having formula M(L A ) p (L B )q (L C ) r In some embodiments of the compound of, ligand L C comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, L C comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, L C comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, L C comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, L C comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0203] In some embodiments of the compound of L having formula I A , at least one R A is not hydrogen. In some embodiments, at least one R A comprises at least one C atom.

[0204] In some embodiments of the compound of L having formula I A , at least one R B is not hydrogen. In some embodiments, at least one R B comprises at least one C atom.

[0205] In some embodiments of the compound of L having 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 joined or fused to one of R A or R B to form a ring, where the ring can be a 5-membered ring. In some embodiments, the 5-membered ring is a pyrrole ring.

[0206] In some embodiments of the compound of L having formula I A , 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.

[0207] In some embodiments of the compound of L having formula I A , L is selected from the group consisting of: BRR', CRR', SiRR', and GeRR'.

[0208] In some embodiments of the compound of L having formula IA In some embodiments of the compound, L is CR.

[0209] In the case of L having formula I A In some embodiments of the compound, the ligand L A is selected from the group consisting of:

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220] wherein X1 to X 19 are each independently C or N;

[0221] wherein each R A and R B independently represents mono-substitution to the maximum possible number of substitutions or no substitution;

[0222] wherein each R A and R B , R e and R f are independently hydrogen or a substituent selected from the group of general substituents as defined herein; and

[0223] wherein each of Y1, Y2 and Y3 is independently selected from the group consisting of: BR e , NR e , PR e , O, S, Se, C═O, S═O, SO2, CR e R f , SiR e R f and GeR e R f ; and any two substituents may be joined or fused to form a ring.

[0224] In some embodiments of the compound, ligand L A may be selected from the group consisting of:

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234] wherein each R1 is independently hydrogen or a substituent selected from the group of general substituents as defined herein;

[0235] The remaining variables are the same as previously defined; and any two substituents may be joined or fused to form a ring.

[0236] In some embodiments of the compound, ligand L A is selected from L Ai , where i is an integer from 1 to 335; and each L Ai is defined as follows:

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270] In the case of having the formula M(L A ) p (LB ) q (L C ) r In some embodiments of the compound of, L B is a substituted or unsubstituted phenylpyridine, and L C is a substituted or unsubstituted acetylacetonate.

[0271] In some embodiments of the compound having the formula M(L A ) p (L B ) q (L C ) r wherein L B and L C are each independently selected from the group consisting of:

[0272]

[0273]

[0274] wherein:

[0275] T is selected from the group consisting of: B, Al, Ga, and In;

[0276] K 1 ' is selected from the group consisting of: a single bond, O, S, NR e , PR e , BR e , CR e R f and SiR e R f ;

[0277] Y 1 to Y 13 each independently is selected from the group consisting of C and N;

[0278] Y' is selected from the group consisting of: 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 GeRe R f ;

[0279] R e and R f may be fused or joined to form a ring;

[0280] Each R a 、R b 、R c and R d independently represents mono-substituted to the maximum allowable number of substitutions or unsubstituted;

[0281] R a1 、R b1 、R c1 、R d1 、R e1 、R a 、R b 、R c 、R d 、R e and R f and each of R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c and R d are independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, selenyl, sulfinyl, sulfonyl, phosphino and combinations thereof; and any two of R

[0282] In some embodiments of a compound having the formula M(L A ) p (L B ) q (L C ) r , L B and L C each independently is selected from the group consisting of:

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290] Wherein:

[0291] R a ', R b ', R c ', R d ' and R e ' each independently represents zero substitution, mono-substitution or up to the maximum allowable number of substitutions on their respective rings;

[0292] R a ', R b ', R c ', R d ' and R e ' each independently is hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, selenyl, sulfinyl, sulfonyl, phosphino and combinations thereof; and

[0293] R a ', R b ', R c ', R d ' and R e ' two of the substituents can be fused or joined to form a ring or form a polydentate ligand.

[0294] In some embodiments of a compound having the formula M(L A ) p (L B ) q (L C ) r wherein L A is selected from L Ai , where i is an integer from 1 to 335; and L B is selected from L Bk , where k is an integer from 1 to 836,

[0295] Wherein:

[0296] When the compound has the formula Ir(L Ai )3, the compound is selected from Ir(L A1 )3 to Ir(LA335 ) A group consisting of 3;

[0297] When the compound has the formula Ir(L Ai )(L Bk )2, the compound is selected from the group consisting of Ir(L A1 )(L B1 )2 to Ir(L A335 )(L B836 )2;

[0298] When 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 );

[0299] When 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 ); and

[0300] When 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 );

[0301] Where each L Bk has a structure defined as follows:

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340] where j is an integer from 1 to 1416, and each L Cj-I has a structure based on the formula ; and

[0341] each L Cj-II has a structure based on the formula where for each L Cj-I and L Cj-II in L Cj , R 201 and R 202 are each independently defined in List 8 below:

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353] where R D1 to R D246 have the structures defined in List 9 below:

[0354]

[0355]

[0356]

[0357] The compounds of the present disclosure may be selected from the group consisting of:

[0358]

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368]

[0369]

[0370]

[0371]

[0372]

[0373]

[0374]

[0375] In some embodiments, a first ligand L of formula I as described herein AThe compound 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 percentage of deuteration has its ordinary meaning and includes the percentage of possible hydrogen atoms (e.g., positions that can be hydrogen or deuterium) replaced by deuterium atoms.

[0376] 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 secondary ligand.

[0377] As used herein, a secondary ligand is a ligand having a higher free ligand T1 energy. The free ligand T1 energy can be determined by a computational program using density functional theory (DFT) modeling. For example, DFT calculations can be performed with the B3LYP functional in the LACVP* basis set. In the first step, the geometry of the complex is optimized while restricting the triplet spin density on each ligand. In the second step, the geometry is re-optimized without imposing the restriction. The spin density should still be localized on the corresponding ligand. The ligand on which the spin density is localized in the lowest energy structure can be regarded as the emissive ligand. If the energy difference between the ligand and the second-ranked ligand is greater than 0.1 eV or 0.20 eV or 0.30 eV, then the ligand is considered the major emissive ligand.

[0378] Effective length of the ligand:

[0379] In some embodiments of the first aspect, each of the first emissive ligand and the secondary ligand has an effective length, and the effective length of the first emissive ligand is at least greater than the effective length of the second ligand

[0380] In some embodiments, ligand L of formula I A has a ligand axis defined as the axis of the bond between ring A and ring B that extends through the ligand.

[0381] Additionally, each ligand L A has a ligand center defined as the midpoint of the bond connecting ring A and ring B. Additionally, each ligand has a ligand bisector defined as an infinite line passing through the metal to the ligand center.

[0382] Additionally, each ligand L A has a length vector defined for each atom in the ligand. Each length vector connects the relevant atom to the ligand center. Further, each ligand L AHaving values L1 and L2, where L1 is the highest value obtained among the products of (the magnitude of the length vector) * (the cosine of the angle formed by the length vector and the ligand axis) on the loop A side of the ligand bisector, and L2 is the highest value obtained among the products of (the magnitude of the length vector) * (the cosine of the angle formed by the length vector and the ligand axis) on the loop B side of the ligand bisector. In these and subsequent calculations (including when parts can rotate around the axis), measurements are made using the molecule in the conformation with the lowest total energy given by geometric optimization in the ground state, and measurements are made using the CEP-31G basis set and DFT in the B3LYP functional.

[0383] The effective length of the ligand is measured as the sum of L1 and L2 of the ligand. The chemical structures shown in Figure 4 are used to show examples of each of these values. Figure 4 The calculated values of L1 and L2 for the example iridium complexes in

[0384] Table 1.

[0385]

[0386]

[0387] 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.

[0388] In some embodiments, the effective length of the first ligand is at least In some embodiments, the effective length of the first ligand is at least

[0389] 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.

[0390] In some embodiments, the molecular weight of the first ligand is at least 100 amu greater than the molecular weight of the second ligand. In some embodiments, the molecular weight of the first ligand is at least 150 amu greater than the molecular weight of the second ligand. In some embodiments, the molecular weight of the first ligand is at least 200 amu greater than the molecular weight of the second ligand.

[0391] In some embodiments, the aliphatic methylene carbons (e.g., CH2) of the first ligand are at least 3 more than those of the second ligand. In some embodiments, the aliphatic methylene carbons of the first ligand are at least 5 more than those of the second ligand. In some embodiments, the aliphatic methylene carbons of the first ligand are at least 8 more than those of the second ligand.

[0392] In some embodiments, the compound comprises a tetradentate ligand formed by one of the first ligand and the second ligand or by the conjugation of the first ligand and the second ligand. In some embodiments, the first ligand and the second ligand conjugate to form a tetradentate ligand.

[0393] 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.

[0394] In some embodiments, the first ligand in the compound contains at least two more R* moieties than the second ligand. In some embodiments, the second ligand contains at least two more R* moieties than the first emitting ligand.

[0395] As used herein, each R* moiety is independently a substituent selected from the group consisting of: halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenoalkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0396] In some embodiments, each R* moiety is independently selected from the group consisting of: halogen, CF3, CN, F, C═O, and OR w , where each R w is independently selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, selenoalkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0397] In some embodiments, the atomic weight of the metal M is greater than 40. In some such embodiments, the metal M is selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu. In some such embodiments, the metal M is Ir or Pt. In some such embodiments, the metal M is Pt.

[0398] In some embodiments, the metal complex compound further comprises a third ligand.

[0399] 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.

[0400] In some embodiments, the first ligand and the third ligand are the same ancillary ligand, and the second ligand is an emissive ligand. In some embodiments, the first ligand and the third ligand are different ancillary ligands, and the second ligand is an emissive ligand. In some embodiments, the second ligand and the third ligand are the same emissive ligand, and the first ligand is an ancillary ligand.

[0401] In some embodiments of the second aspect, the second vector F2 forms an angle greater than 45 degrees with F1.

[0402] In cases where more than one pair of atoms meets the requirements for the first binding vector M1, the pair that forms the longest first binding vector meeting the other requirements is selected. In cases where more than one pair of atoms meets the requirements for the second binding vector M2, the pair that forms the longest second binding vector meeting the other requirements is selected.

[0403] In some embodiments, the complex compound has a first free vector F1, which is represented by a first binding vector M1 that connects any two atoms in the compound and passes through within the metal and has a length greater than ; wherein the compound has a second free vector F2, which is represented by a second binding vector M2 that connects any two atoms in the compound and has a length greater than ; and wherein the angle between the emission transition dipole moment vector and the cross product of the vectors F1 and F2 is less than 45 degrees. ; and wherein the angle between the emission transition dipole moment vector and the cross product of the vectors F1 and F2 is less than 45 degrees.

[0404] In some embodiments, the atoms forming the second binding vector M2 are in the same ligand, and the atoms forming the first binding vector M1 are in different ligands. In some embodiments, the atoms forming the second binding vector M2 are in a ligand different from any of the atoms forming the first binding vector M1.

[0405] In some embodiments, the second vector F2 forms an angle greater than 45 degrees with F1.

[0406] 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.

[0407] In some embodiments of the second aspect, the lengths of both F1 and F2 are greater than In some embodiments of the second aspect, the lengths of both F1 and F2 are greater than

[0408] In some embodiments, the angle between the emission 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 emission transition dipole moment vector and the cross product of the vectors F1 and F2 is less than 20 degrees.

[0409] In some embodiments, the compound has a plane P defined by free vectors F1 and F2, the free vectors being represented by corresponding bound vectors M1 and M2, and the plane P being parallel to M1 and M2 and passing through the metal M; and 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 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 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

[0410] The perpendicular distance from a point to the plane P is calculated using the standard formula for the distance of a point from a plane:

[0411]

[0412] where a, b, c are the components of the plane normal vector, x0, y0, z0 are the coordinates of the atom, and d is the constant of the plane equation that ensures the plane passes through the metal atom.

[0413] 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 percentage of deuteration has its ordinary meaning and includes the percentage of possible hydrogen atoms (e.g., positions that can be hydrogen or deuterium) replaced by deuterium atoms.

[0414] C. OLEDs and Devices of the Present Disclosure

[0415] In another aspect, the present disclosure also provides an OLED device comprising a first organic layer containing a compound as disclosed in the above compound portion of the present disclosure.

[0416] In some embodiments, the OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a metal coordination complex compound as described herein.

[0417] In some embodiments, the organic layer can be an emissive layer and the compound as described herein can be an emissive dopant or a non-emissive dopant.

[0418] 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.

[0419] 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.

[0420] 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.

[0421] In some embodiments, the organic layer can further comprise a host, wherein the host comprises a triphenylene containing a benzo-fused thiophene or a benzo-fused furan, wherein any substituent in the host is independently a non-fused substituent selected from the group consisting of: C n H 2n+1 、OC n H 2n+1 、OAr1、N(C n H 2n+1 )2、N(Ar1)(Ar2)、CH=CH-C n H 2n+1 、C≡CC n H 2n+1 、Ar1、Ar1-Ar2、C n H 2n -Ar1 or unsubstituted, where n is an integer from 1 to 10; and wherein Ar1 and Ar2 are independently selected from the group consisting of: benzene, biphenyl, naphthalene, triphenylene, carbazole and their heteroaromatic analogs.

[0422] In some embodiments, the organic layer can further comprise a host, wherein the host comprises 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).

[0423] In some embodiments, the host can be selected from the host group 1 consisting of:

[0424]

[0425]

[0426]

[0427]

[0428]

[0429]

[0430]

[0431]

[0432] Wherein:

[0433] X 1 to X 24 Each independently is C or N;

[0434] L' is a direct bond or an organic linking group;

[0435] Each Y A Independently selected from the group consisting of: no bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, BRR';

[0436] R A ', R B ', R C ', R D ', R E ', R F ' and R G ' Each independently represents mono-substituted to maximum substitution or unsubstituted;

[0437] Each R, R', R A ', R B', R C ', R D ', R E ', R F ' and R G ' and R are independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, boranyl, and combinations thereof;

[0438] R A ', R B ', R C ', R D ', R E ', R F ' and R G Any two of ', R', ', R', ', R', ', R', ', R', ', R', ', R', ', R', and R' are optionally joined or fused to form a ring.

[0439] In some embodiments, the host may be selected from the following host group 2:

[0440]

[0441]

[0442]

[0443] and combinations thereof.

[0444] In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.

[0445] In some embodiments, the compounds as described herein may be sensitizers; wherein the device may further comprise a receptor; and wherein the receptor may be selected from the group consisting of: fluorescent emitters, delayed fluorescent emitters, and combinations thereof.

[0446] In yet another aspect, the OLED of the present disclosure may further comprise an emission region containing a compound as disclosed in the above compound portion of the present disclosure.

[0447] In some embodiments, the emission region may comprise a metal coordination complex compound as described herein.

[0448] In some embodiments, at least one of an anode, a cathode, or a new layer disposed above the organic emission layer serves as an enhancement layer. The enhancement layer comprises a plasmonic material that exhibits surface plasmon resonance, the plasmonic material being non-radiatively coupled to an emitter material and transferring excited state energy from the emitter material to a non-radiative mode of surface plasmon polaritons. The enhancement layer is disposed at a distance not exceeding a threshold distance from the organic emission layer, wherein due to the presence of the enhancement layer, the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant, and the threshold distance is the location where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed above the enhancement layer on the opposite side of the organic emission layer. In some embodiments, the outcoupling layer is disposed on the side of the emission layer opposite to the enhancement layer but is still capable of outcoupling the energy of the surface plasmon mode from the enhancement layer. The outcoupling layer scatters the energy from the surface plasmon polaritons. In some embodiments, this energy is scattered as photons into free space. In other embodiments, the energy is scattered from the surface plasmon mode of the device into other modes, such as but not limited to organic waveguide modes, substrate modes, or another waveguide mode. If the energy is scattered into a non-free space mode of the OLED, other outcoupling schemes can be combined to extract the energy into free space. In some embodiments, one or more intermediate layers can be disposed between the enhancement layer and the outcoupling layer. Examples of intermediate layers can be dielectric materials, including organic, inorganic, perovskite, oxides, and can include stacks and / or mixtures of these materials.

[0449] The enhancement layer changes the effective properties of the medium in which the emitter material resides, thereby causing any one or all of the following: reduced emissivity, altered emission line shape, angular variation of emission intensity, altered emitter material stability, altered OLED efficiency, and reduced roll-off efficiency of the OLED device. Placing the enhancement layer on the cathode side, the anode side, or both sides results in an OLED device that exploits any of the above effects. In addition to the specific functional layers described in the various OLED examples mentioned herein and illustrated in the figures, the OLEDs according to the present disclosure can also include any other functional layers common in OLEDs.

[0450] The enhancement layer may include 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 the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. Generally, a metamaterial is a medium composed of different materials, where the medium as a whole acts differently from the sum of its material parts. Specifically, we define an optically active metamaterial as a material that simultaneously has a negative permittivity and a negative permeability. On the other hand, a hyperbolic metamaterial is an anisotropic medium in which the permittivity or permeability has different signs for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly different from many other photonic structures, such as Distributed Bragg Reflectors (“DBR”), because on the length scale of the optical wavelength, the medium should appear uniform in the propagation direction. Using terms understandable to those skilled in the art: the dielectric constant of the metamaterial in the propagation direction can be described by an effective medium approximation. Plasmonic materials and metamaterials provide methods for controlling light propagation, which can enhance OLED performance in various ways.

[0451] In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has features of wavelength size arranged periodically, quasi-periodically, or randomly, or has features of sub-wavelength size arranged periodically, quasi-periodically, or randomly. In some embodiments, the features of wavelength size and sub-wavelength size have sharp edges.

[0452] In some embodiments, the outer coupling layer has features of wavelength size arranged periodically, quasi-periodically, or randomly, or has features of sub-wavelength size arranged periodically, quasi-periodically, or randomly. In some embodiments, the outer coupling layer may be composed of a plurality of nanoparticles, and in other embodiments, the outer coupling layer is composed of a plurality of nanoparticles disposed above a material. In these embodiments, the outer coupling can be adjusted by at least one of the following methods: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, changing the thickness of the enhancement layer, and / or changing the material of the enhancement layer. The plurality of nanoparticles of the device can be formed by at least one of the following: metal, dielectric material, semiconductor material, metal alloy, mixture of dielectric materials, stack or layer of one or more materials, and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the outer coupling layer is composed of at least metal nanoparticles, where the metal is selected from the group consisting of: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. The plurality of nanoparticles can have an additional layer disposed above them. In some embodiments, the outer coupling layer can be used to adjust the polarization of the emission. Changing the size and periodicity of the outer coupling layer can select the polarization type that is preferentially outer-coupled to air. In some embodiments, the outer coupling layer also serves as an electrode of the device.

[0453] In yet another aspect, the present disclosure also provides a consumer product that includes an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer can include a compound as disclosed in the above compound portion of the present disclosure.

[0454] In some embodiments, the consumer product includes an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer can include a metal coordination complex compound as described herein.

[0455] In some embodiments, the consumer product can be one of the following products: a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a lamp for interior or exterior illumination and / or signaling, a head-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cellular telephone, a tablet computer, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a video camera, a viewfinder, a microdisplay having a diagonal of less than 2 inches, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising a plurality of tiled together displays, a theater or stadium screen, a light therapy device, and a sign.

[0456] 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. The injected holes and electrons each migrate toward the electrode of opposite charge. When an electron and a hole are located on the same molecule, an “exciton” is formed, which is a localized electron-hole pair having an excited energy state. When the exciton relaxes through a light-emission mechanism, light is emitted. In some cases, the exciton can be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, can also occur, but are generally considered undesirable.

[0457] Several OLED materials and configurations are described in U.S. Patent Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entireties.

[0458] Initial OLEDs used emissive molecules that emit light from singlet states (“fluorescence”), as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission typically occurs within a time frame of less than 10 nanoseconds.

[0459] Recently, OLEDs having emissive materials that emit light from triplets (“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”), which are hereby incorporated by reference in their entirety. Phosphorescence is described in more detail in U.S. Patent No. 7,279,704, columns 5 - 6, which is hereby incorporated by reference.

[0460] Figure 1 An organic light-emitting device 100 is shown. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers in sequence. The properties and functions of these various layers and exemplary materials are described in more detail in U.S. 7,279,704, columns 6 - 10, which is hereby incorporated by reference.

[0461] More instances of each of these layers can be obtained. For example, a 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 m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of light-emitting 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 BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which disclosure 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 that include a composite cathode having a thin layer of metal (such as Mg:Ag) with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use of the barrier layer 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. An example of an injection layer is 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.

[0462] Figure 2 Displays an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by depositing the layers in sequence. Since the most common OLED configuration has a cathode disposed above the anode, and 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 with respect to the device 100 can be used in the corresponding layers of the device 200. Figure 2 Provides an example of how some of the layers can be omitted from the structure of the device 100.

[0463] Figure 1 and 2The simple layer structure described herein is provided by way of non-limiting example, and it should be understood that embodiments of the present disclosure may be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be obtained by combining the various layers described in different ways, or the layers may be completely omitted based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe the various layers as including a single material, it should be understood that combinations of materials may be used, such as a mixture of a host and a dopant, or more generally, mixtures. In addition, the layers may have various sub-layers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, the hole transport layer 225 transports holes and injects holes into the emission layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials such as, for example, as described with respect to Figure 1 and 2 the different organic materials.

[0464] Structures and materials not specifically described may also be used, such as OLEDs (PLEDs) comprising polymeric materials, as disclosed, for example, in U.S. Patent No. 5,247,190 to Friend et al., which is incorporated herein by reference in its entirety. By way of another example, an OLED having a single organic layer may be used. OLEDs may be stacked, for example, as described in U.S. Patent No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. The OLED structure may deviate from Figure 1 and 2 the simple layer structure described therein. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as the mesa structure described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the dimpled structure described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated herein by reference in their entirety.

[0465] Unless otherwise specified, any one of the layers of the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet (as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entirety), organic vapor phase deposition (OVPD) (as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety), and deposition by organic vapor jet printing (OVJP, also known as organic vapor jet deposition (OVJD)) (as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding (as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety), and patterning associated with some of the deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods can also be used. The materials to be deposited can be modified to be suitable for a particular deposition method. For example, branched or unbranched substituents, preferably containing at least 3 carbons such as alkyl and aryl groups, can be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 or more carbons can be used, and a range of 3 to 20 carbons is preferred. Materials having an asymmetric structure can have better solution processability than materials 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 withstand solution processing.

[0466] Devices fabricated in accordance with embodiments of the present disclosure may further optionally include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage by harmful substances in an environment that includes moisture, vapor, and / or gases, etc. The barrier layer may be deposited on the substrate, on the electrodes, under the substrate, under the electrodes, beside the substrate, beside 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 compounds or organic compounds or both. Preferred barrier layers include mixtures of polymeric materials 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 incorporated herein by reference in their entirety. In order to be considered a "mixture", the foregoing polymeric and non-polymeric materials that make up 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 may range from 95:5 to 5:95. The polymeric material and the non-polymeric material may be produced from the same precursor material. In one example, the mixture of the polymeric material and the non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

[0467] Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units), which can in turn be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels) that can be utilized by end-user product manufacturers, and the like. The electronic component module can optionally include drive electronics and / or a power source. Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. Disclosed is a consumer product that includes an OLED which includes a compound of the present disclosure in an organic layer of the OLED. The consumer product should include any type of product that includes one or more of one or more light sources and / or some type of visual display. Some examples of the consumer product include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular telephones, tablet computers, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays (displays having a diagonal less than 2 inches), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple tiled together displays, theater or stadium screens, light therapy devices, and signs. A variety of control mechanisms can be used to control the devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as from 18 °C to 30 °C, and more preferably at room temperature (20 - 25 °C), but can be used outside of this temperature range (e.g., from -40 °C to +80 °C).

[0468] More details regarding OLEDs and the definitions described above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0469] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can employ the materials and structures. More generally, organic devices such as organic transistors can employ the materials and structures.

[0470] In some embodiments, the OLED has one or more characteristics selected from the group consisting of: flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further includes a layer comprising carbon nanotubes.

[0471] In some embodiments, the OLED further includes a layer comprising a delayed fluorescence emitter. In some embodiments, the OLED includes an RGB pixel arrangement or a white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal 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 at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0472] In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can generate emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-type delayed fluorescence, see, e.g., U.S. Application No. 15 / 700,352, which is incorporated herein by reference in its entirety), triplet-triplet annihilation, or a combination of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from the others). In some embodiments, when there is more than one ligand coordinated to the metal, the ligands can all be the same. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, each ligand can be different from one another. This also holds true in embodiments where the ligands coordinated to the metal can be linked to other ligands coordinated to the metal to form tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, in the case where the coordinating ligands are linked together, in some embodiments all the ligands can be the same, and in some other embodiments at least one of the linked ligands can be different from the other ligand(s).

[0473] In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED, wherein one or more layers in the OLED contain a receptor in the form of one or more fluorescent and / or delayed fluorescence emitters. In some embodiments, the compound can be used as a component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to the receptor and the receptor will emit energy or further transfer energy to the final emitter. The receptor concentration can range from 0.001% to 100%. The receptor can be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the receptor is a TADF emitter. In some embodiments, the receptor is a fluorescent emitter. In some embodiments, the emission can be generated by any one or all of the sensitizer, the receptor, and the final emitter.

[0474] According to another aspect, a formulation comprising the compounds described herein is also disclosed.

[0475] The OLEDs disclosed herein can be incorporated into one or more of consumer products, electronic component modules, and lighting panels. The organic layer can be an emissive layer, and the compound can be an emissive dopant in some embodiments and a non-emissive dopant in other embodiments.

[0476] In yet another aspect of the present invention, 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.

[0477] The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure or their monovalent or polyvalent variants. In other words, the compounds of the present invention or their monovalent or polyvalent variants can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of monomers, polymers, macromolecules, and supramolecules (also known as supermolecules). As used herein, a "monovalent variant of a compound" refers to a compound that is the same as the compound but one hydrogen has been removed and replaced with a moiety that forms a bond to the rest of the chemical structure. As used herein, a "polyvalent variant of a compound" refers to a compound that is the same as the compound but more than one hydrogen has been removed and replaced with one or more moieties that form bonds to the rest of the chemical structure. In the case of supramolecules, the compounds of the present invention can also be incorporated into supramolecular complexes without covalent bonds.

[0478] D. Combinations of the Compounds of the Present Disclosure with Other Materials

[0479] Materials described herein as suitable for use in a particular layer in an organic light emitting device may be used in combination with a variety of other materials present in the device. For example, the emissive dopants disclosed herein may 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 mentioned below are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that may be used in combination.

[0480] a) Conductive dopants:

[0481] The charge transport layer may be doped with a conductive dopant to substantially change its charge carrier density, which in turn will change 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 may be doped with a p-type conductive dopant, and an n-type conductive dopant is used in the electron transport layer.

[0482] Non-limiting examples of conductive dopants that may be used in combination with the materials disclosed herein in an OLED, along with the references that disclose those materials, are illustrated below: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.

[0483]

[0484]

[0485] b) HIL / HTL:

[0486] The hole injection / transport materials used in this disclosure are not particularly limited, and any compound may be used as long as the compound is commonly used as a hole injection / transport material. Examples of materials include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; fluorocarbon-containing polymers; polymers with conductive dopants; conductive polymers such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x; p-type semiconductive organic compounds such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes; and crosslinkable compounds.

[0487] Examples of aromatic amine derivatives for HIL or HTL include (but are not limited to) the following general structures:

[0488]

[0489] Ar 1 to Ar 9 each of which is selected from the group consisting of: aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, fluorene, phenanthrene, fluoranthene, pyrene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are the same type or different types of groups selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are bonded to each other 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 ring group. Each Ar may be unsubstituted or may be substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio group, sulfinyl, sulfonyl, phosphino group, and combinations thereof.

[0490] In one aspect, Ar 1 to Ar 9 are independently selected from the group consisting of:

[0491]

[0492] where k is an integer from 1 to 20; X 101 to X 108 is C (including CH) or N; Z 101 is NAr 1, O or S; Ar 1 having the same groups as defined above.

[0493] Examples of metal complexes used in HIL or HTL include (but are not limited to) the following general formulae:

[0494]

[0495] wherein Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 are independently selected from C, N, O, P and S; L 101 is an ancillary ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0496] In one aspect, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. In another aspect, (Y 101 -Y 102 ) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os and Zn. In another aspect, the metal complex has a minimum oxidation potential in solution of less than about 0.6 V compared to the Fc + / Fc couple.

[0497] Non-limiting examples of HIL and HTL materials that can be combined with the materials disclosed herein for use in OLEDs are illustrated below together with the references disclosing those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, 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, WO2014030921,WO2014034791, WO2014104514, WO2014157018.

[0498]

[0499]

[0500]

[0501]

[0502]

[0503]

[0504] c) EBL:

[0505] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emissive layer. The presence of such a blocking layer in the device can result in generally higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. Additionally, a blocking layer can be used to confine emission to the 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 compared to 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 compared to 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 one used in the host described below.

[0506] d) Host:

[0507] 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 a 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.

[0508] Examples of the metal complex used as a host preferably have the following general formula:

[0509]

[0510] where Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal; and k' + k" is the maximum number of ligands that can be connected to the metal.

[0511] In one aspect, the metal complex is:

[0512]

[0513] where (O-N) is a bidentate ligand having a metal coordinated to the O and N atoms.

[0514] In another aspect, Met is selected from Ir and Pt. In another aspect, (Y 103 -Y 104 ) is a carbene ligand.

[0515] In one aspect, the host compound contains at least one selected from the following groups: the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, picene, phenanthrene, fluorene, pyrene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units, which are the same type or different types of groups selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are bonded to each other 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 ring group. Each option in each group may be unsubstituted or may be substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio group, sulfinyl, sulfonyl, phosphino group, and combinations thereof.

[0516] In one aspect, the host compound contains at least one of the following groups in the molecule:

[0517]

[0518]

[0519] wherein R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino and combinations thereof, and when it is aryl or heteroaryl, it has a definition similar to Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20. X 101 to 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.

[0520] Non-limiting examples of host materials that can be combined with the materials disclosed herein for use in OLEDs are illustrated below together with the references disclosing 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,

[0521]

[0522]

[0523]

[0524]

[0525]

[0526] e) Other emitters:

[0527] One or more other emitter dopants may be used in combination with the compounds of the present invention. Examples of other emitter dopants are not particularly limited, and any compound may be used as long as the compound is generally used as an emitter material. Examples of suitable emitter materials include (but are not limited to) compounds that can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0528] Non-limiting examples of emitter materials that can be combined with the materials disclosed herein for use in OLEDs are illustrated below together with the references disclosing 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.

[0529]

[0530]

[0531]

[0532]

[0533]

[0534]

[0535] f) HBL:

[0536] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons leaving the emissive layer. The presence of such a blocking layer in the device can result in generally higher efficiency and / or longer lifetime compared to a similar device lacking the blocking layer. Additionally, a blocking layer can be used to confine 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 a higher triplet energy compared to the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and / or a higher triplet energy compared to one or more of the hosts closest to the HBL interface.

[0537] In one aspect, the compounds used in the HBL contain the same molecules or the same functional groups as those used in the host described above.

[0538] In another aspect, the compounds used in the HBL contain at least one of the following groups in the molecule:

[0539]

[0540] where k is an integer from 1 to 20; L 101 is another ligand and k' is an integer from 1 to 3.

[0541] g) ETL:

[0542] The electron transport layer (ETL) can include materials capable of transporting electrons. The electron transport layer can be intrinsic (undoped) or 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 commonly used to transport electrons.

[0543] In one aspect, the compounds used in the ETL contain at least one of the following groups in the molecule:

[0544]

[0545] where R 101Selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino and combinations thereof, and when it is aryl or heteroaryl, it has a definition similar to Ar as described above. Ar 1 to Ar 3 has a definition similar to Ar mentioned above. k is an integer from 1 to 20. X 101 to X 108 is selected from C (including CH) or N.

[0546] In another aspect, the metal complex used in the ETL contains (but is not limited to) the following general formula:

[0547]

[0548] where (O-N) or (N-N) is a bidentate ligand having a metal coordinated to atoms O, N or N, N; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal.

[0549] Non-limiting examples of ETL materials that can be combined with the materials disclosed herein for use in OLEDs, along with references disclosing those materials, are illustrated below: 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,

[0550]

[0551]

[0552]

[0553] h) Charge Generation Layer (CGL)

[0554] In a tandem or stacked OLED, the CGL plays a fundamental role in performance and is composed of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied by the CGL and the electrodes. The electrons and holes consumed in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductive dopants used in the transport layer.

[0555] In any of the above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. The minimum amount of deuterated hydrogen in the compound is selected from the group consisting of: 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% and 100%. Thus, any specifically listed substituent, such as (but not limited to) methyl, phenyl, pyridyl, etc. can be in its non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (such as (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) can also be in their non-deuterated, partially deuterated, and fully deuterated forms.

[0556] It should be understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the 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. The invention as claimed may thus include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that the various theories as to why the invention works are not intended to be limiting.

[0557] E. Experimental data

[0558] To determine the VDR, a film for angle-dependent photoluminescence was fabricated by vacuum thermal evaporation of an optional H2 layer on a UV ozone-pretreated glass substrate, followed by an H1 or H3 doped with 3-5% emitter. Subsequently, the photoluminescence related to the polarization angle was measured using a Fluxim Phelos system with a 340 nm or 405 nm excitation source and fitted with Setfos software to obtain the VDR. The relationship of the Phelos spectral intensity with respect to the angle was obtained by integrating over the wavelength range within the range excluding the excitation source scattering. The fitting routine within Setfos is as follows. The optical stack was set to be the same as the experiment using a 0.7 mm glass substrate that measures the emission, a 40 nm EML film with an emitter, and air as the final layer. The emitter distribution was set exponentially, with its position at the top air-EML interface and a width of 50 nm. The relationships of the integrated p-polarized and s-polarized spectral intensities with the angle were used as the input targets for the Setfos fitting / optimization routine. The optimized fitting parameters were: emitter orientation (VDR), emission intensity, and EML refractive index. The VDR obtained from this fitting was the reported value, where VDR = vertical dipole ratio (0.33 is random, and any value less than 0.33 has a net horizontal alignment).

[0559] Table 6

[0560] Table 6

[0561]

[0562]

[0563] Among them, the structures of E1-43 and H1-3 are as follows:

[0564]

[0565]

[0566]

[0567]

[0568]

[0569]

[0570] Compared with the comparative examples (CE) listed in the table, these experimental VDR results in Table 6 represent the criteria for achieving a VDR complex > 0.33 as claimed herein.

[0571] Synthesis Examples

[0572] Synthesis of 5-fluoro-2-(m-tolyl)pyridine:

[0573]

[0574] 2-Chloro-5-fluoropyridine (3.90 g, 3.000 mL, 1 equiv, 29.7 mmol), m-tolylboronic acid (6.05 g, 1.5 equiv, 44.5 mmol), Pd(PPh3)4 (1.71 g, 0.05 equiv, 1.48 mmol) and potassium carbonate (8.20 g, 2 equiv, 59.3 mmol) were combined in dioxane (75.00 mL) and water (25.00 mL), and heated under reflux for 16 h. The mixture was diluted with water and brine and extracted with EtOAc. After concentration under drying and vacuum, the mixture was purified by column chromatography to give the product as a colorless oil, 5.15 g (93%).

[0575] Synthesis of 5-neopentyl-1-phenyl-1H-pyrazole:

[0576]

[0577] Under nitrogen, 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), and a solution of neopentylzinc bromide (II) 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. Extracted with EtOAc, then dried, purified by column chromatography, and additionally wet-milled in heptane to give the product as a white solid, yield 1.77 g (45%).

[0578] Synthesis of 4-bromo-5-neopentyl-1-phenyl-1H-pyrazole:

[0579]

[0580] A solution of 5-neopentyl-1-phenyl-1H-pyrazole (5.700 g, 1 equiv, 26.60 mmol) in MeCN (150.00 mL) was cooled in an ice / water bath, and solid 1-bromopyrrolidine-2,5-dione (4.970 g, 1.05 equiv, 27.93 mmol) was added, and the solution was allowed to warm to room temperature over 16 h. The reaction mixture was concentrated in vacuo and purified by column chromatography to give a slowly solidifying colorless oil, 6.21 g (80%).

[0581] Synthesis of 5-neopentyl-1,4-diphenyl-1H-pyrazole:

[0582]

[0583] A solution of 4-bromo-5-neopentyl-1-phenyl-1H-pyrazole (3.250 g, 1 equiv, 11.08 mmol), phenylboronic acid (3.379 g, 2.5 equiv, 27.71 mmol) and potassium carbonate (6.127 g, 4 equiv, 44.34 mmol) in dioxane (50.00 mL) and water (25.00 mL) was bubbled with nitrogen for 10 min. Pd2(dba)3 (203.0 mg, 0.02 equiv, 221.7 μmol) and S-Phos (364.0 mg, 0.08 equiv, 886.7 μmol) were added, and the reaction mixture was heated at reflux for 16 h. The reaction was diluted with water and extracted with EtOAc, and the organic phase was concentrated in vacuo. Purification by column chromatography gave the product as a white solid, 3.03 g (94%).

[0584] Synthesis of iridium dimer:

[0585]

[0586] A suspension of 5-neopentyl-1,4-diphenyl-1H-pyrazole (1.871 g, 4.6 eq, 6.441 mmol) and iridium(III) chloride hydrate (1.038 g, 2 eq, 2.801 mmol) in 2-ethoxyethanol (30.00 mL) and water (10.00 mL) was bubbled with nitrogen for 15 minutes and then heated under reflux for 16 hours. The mixture was cooled to room temperature and MeOH was added. It was filtered and washed with more MeOH to give the dimer as an off-white solid, 2.27 g (quantitative).

[0587] Synthesis of iridium solvate triflate:

[0588]

[0589] A suspension of iridium dimer (4.000 g, 0.5 eq, 2.480 mmol) in DCM (105.0 mL) was added to a solution of oxo((trifluoromethyl)sulfonyl)silver (1.306 g, 1.025 eq, 5.084 mmol) in MeOH (15.00 mL). The reaction mixture was stirred at room temperature for 16 hours covered with foil. It was filtered through Celite and then concentrated in vacuo to give the iridium solvate triflate as a beige foam in quantitative yield.

[0590] Synthesis of E31:

[0591]

[0592] A solution of iridium solvate triflate (0.600 g, 1 eq, 652 μmol) and 5-fluoro-2-(m-tolyl)pyridine (0.230 g, 1.88 eq, 1.23 mmol) in acetone (20.00 mL) was bubbled with nitrogen for 10 minutes, then triethylamine (132 mg, 182 μL, 2 eq, 1.30 mmol) was added. The mixture was heated under reflux for 16 hours and then concentrated in vacuo. The residue was dissolved in 200 mL of THF and bubbled with nitrogen, then irradiated with 405 nm light for 2 hours. The solution was concentrated again in vacuo and purified by column chromatography to give E31, 0.40 g (64%).

Claims

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

42.

2. The compound according to claim 1, wherein the VDR of the compound is > 0.35; and / or wherein the spin density population of the first emitting ligand is > 70%; and / or wherein the NTO particle population of the first emitting ligand is > 60%; and / or wherein the LC of the first emitting ligand is > 40%; and / or wherein the complex LLCT of the first emitting ligand is < 30%; and / or wherein the M / T ratio of the first emitting ligand is > 0.44; and / or Wherein the first emissive ligand comprises a polycyclic fused ring system coordinated to the metal.

3. The compound of claim 1, wherein the compound further comprises a second ligand coordinated to the metal; and / or wherein each of the first emitting ligand and the second ligand has an effective length, and wherein the effective length of the first emitting ligand is at least and / or wherein the first emitting ligand has at least 5 more non-hydrogen atoms than the second ligand; and / or wherein the molecular weight of the first emissive ligand is at least 100 amu greater than the molecular weight of the second ligand; and / or The number of aliphatic methylene carbon atoms in the first emitting ligand is at least 3 more than that in the second ligand.

4. The compound of claim 1, wherein the compound further comprises a second ligand coordinated to the metal; wherein the compound has a first free vector F1 formed by connecting any two atoms in the compound and in the metal The inner part is represented by the bound vector M1, and the length of the bound vector M1 is greater than wherein the compound has a second free vector F2 represented by a bound vector M2 connecting any two atoms in the compound; The length of the binding vector M2 is greater than and The compound has a transition dipole moment vector, and the angle between the transition dipole moment vector and the cross product of vectors F1 and F2 is less than 45 degrees.

5. The compound of claim 1, wherein the compound further comprises a second ligand coordinated to the metal; wherein the compound has two metal coordination bonds in trans configuration; wherein the compound has a first vector W1 formed between any atom on the periphery of the compound and the metal; wherein the compound has a second vector W2 formed between any other atom on the periphery of the compound and the metal; wherein each magnitude of W1 and W2 is greater than and The compound has an emission transition dipole moment vector, and the angle between the emission transition dipole moment vector and the cross product of vectors W1 and W2 is less than 45 degrees.

6. The compound according to claim 1, wherein the compound has the formula M(L A ) p (L B ) q (L C ) r , where L B and L C each is a bidentate ligand; and wherein p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; And p+q+r is the oxidation state of metal M.

7. The compound according to claim 6, wherein the compound has a formula selected from the group consisting of: Ir(L A )3、Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )2(L C ) and Ir(L A )(L B )(L C ); and where L A , L B and L C Different from each other.

8. The compound according to claim 7, wherein the ligand L A Select from the group consisting of: Where X1 to X 19 each independently is C or N; Each R A and R B independently represents monosubstitution 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 as defined herein; and wherein each of Y1, Y2 and Y3 is independently selected from the group consisting of: BR e NR e , PR e , O, S, Se, C=O, S=O, SO2, CR e R f 、SiR e R f and GeR e R f ;and Any two substituents may be joined or fused to form a ring.

9. The compound according to claim 6, wherein the ligand L A Selected from L Ai , where i is an integer from 1 to 335; And each L Ai The definition is as follows:

10. The compound according to claim 6, wherein L B and L C Each independently selected from the group consisting of: in: T is selected from the group consisting of B, Al, Ga and In; K 1 'Selected from the group consisting of: single bond, O, S, NR e , PR e , BR e , CR e R f and SiR e R f ; Y 1 To Y 13 Each of which is independently selected from the group consisting of C and N; Y'Select from the group consisting of: 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 ; R e and R f may be fused or joined to form a ring; Each R a , R b , R c and R d independently represents monosubstituted to the maximum allowed 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 of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thiol, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and R a1 , R b1 , R c1 , R d1 , R a , R b , R c and R d Any two substituents in may be fused or joined to form a ring or to form a multidentate ligand.

11. The compound according to claim 7, wherein L A Selected from L Ai , where i is an integer from 1 to 335; and L B Selected from L Bk , where k is an integer from 1 to 836, in: When the compound has the formula Ir(L Ai )3, the compound is selected from Ir(L A1 )3 to Ir(L A335 )3; When the compound has the formula Ir(L Ai )(L Bk )2, the compound is selected from Ir(L A1 )(L B1 )2 to Ir(L A335 )(L B836 )2; When the compound has the formula Ir(L Ai )2(L Bk ), the compound is selected from Ir(L A1 )2(L B1 ) to Ir(L A335 )2(L B836 ) When the compound has the formula Ir(L Ai )2(L Cj-I ), the compound is selected from Ir(L A1 )2(L C1-I ) to Ir(L A335 )2(L C1416-I ); and When the compound has the formula Ir(L Ai )2(L Cj-II ), the compound is selected from Ir(L A1 )2(L C1-II ) to Ir(L A335 )2(L C1416-II ) Each L Bk With a structure defined like this: Where j is an integer from 1 to 1416, and each L Cj-I Based on the formula structure; and Each L Cj-II Based on the formula The structure of Cj-I and L Cj-II Each L Cj , R 201 and R 202 Each is independently defined in Listing 8 below: Where R D1 to R D246 With the following structure defined in Listing 9:

12. The compound of claim 1, wherein the compound is selected from the group consisting of:

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

42.

14. The OLED of claim 13, wherein the OLED further comprises an enhancement layer, wherein the enhancement layer comprises a plasmonic material that exhibits a surface plasmon resonance, the plasmonic material non-radiatively couples to an emitter material and transfers excited state energy from the emitter material to a non-radiative mode of a surface plasmon polariton.

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

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