Organic electroluminescent materials and devices

Abstract

To provide organic materials suitable for applications such as emitters in organic light emitting diodes and related electronic devices.SOLUTION: The invention provides compounds of formula Ir(LA)x(LB)y(LC)z. (x and y are each independently 1 or 2 and z is 0 or 1 while satisfying x+y+z=3; first ligand LA includes the structure of the upper formula in the figure; ligand LB includes the structure of the lower formula; and ligand LC is a bidentate ligand.)SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. patent application Ser. No. 18 / 239,358 (filed Aug. 29, 2023), Ser. No. 18 / 666,894 (filed May 17, 2024), Ser. No. 18 / 537,854 (filed Dec. 13, 2023), Ser. No. 18 / 457,006 (filed Aug. 28, 2023), and Ser. No. 18 / 44 No. 9,951 (filed on August 15, 2023), No. 18 / 657,918 (filed on May 8, 2024), No. 18 / 657,900 (filed on May 8, 2024) No. 18 / 666,935 (filed on May 17, 2024), No. 18 / 811,489 (filed on August 21, 2024) , No. 18 / 666,918 (filed on May 17, 2024), No. 17 / 844,331 (filed on June 20, 2022), No. 18 / 297 , No. 781 (April 10, 2023), No. 18 / 461,744 (filed on September 6, 2023) No. 18 / 058,461 (November 2022) No. 18 / 058,556 (filed Nov. 23, 2022), No. 18 / 438,528 (filed Feb. 12, 2024), No. 18 / 414,644 (filed Jan. 17, 2024), and No. 18 / 669,672 (filed May 21, 2024). This application is a continuation-in-part of any of the above applications, either directly or through any of the above applications, and is not a continuation-in-part application of any of the above applications pursuant to 35 U.S.C. § 119(e). Based on U.S. Provisional Application Nos. 63 / 614,955 (filed December 27, 2023), 63 / 625,704 (filed January 26, 2024), 63 / 620,548 (filed January 12, 2024), 63 / 562,444 (filed March 7, 2024), 63 / 664,204 (filed June 26, 2024), 63 / 566,737 (filed March 18, 2024), and 63 / 565,596 (filed March 15, 2024) , No. 63 / 644,316 (filed on May 8, 2024), No. 63 / 668,357 (filed on July 8, 2024), No. 63 / 658,601 (filed on June 11, 2024), No. 63 / 660,831 (filed on June 11, 2024) 63 / 664,598 (filed on June 26, 2024), 63 / 662,065 (filed on June 20, 2024), 63 / 671,920 (filed on July 16, 2024), 63 / 675,No. 452 (filed on July 25, 2024), No. 63 / 678,268 (filed on August 1, 2024), No. 63 / 682,977 (filed on August 14, 2024), No. 63 / 638,792 (filed on April 2024) (filed on April 25, 2024), No. 63 / 632,798 (filed on April 11, 2024), No. 63 / 573,092 (filed on April 2, 2024), No. 63 / 627,131 (filed on January 31, 2024), No. 63 / 606,898 (filed on December 6, 2023), No. 63 / 592,426 (filed on October 23, 2023), No. 63 / 579,652 (filed on August 30, 2023), No. 63 / 515,210 (July 24, 2023), No. 63 / 504,507 (filed on May 26, 2023), No. 63 / 216,339 (filed on June 29, 2021), No. 63 / 497,148 (filed on April 19, 2023) ), No. 63 / 459,773 (filed on April 17, 2023), No. 63 / 459,415 (filed on April 14, 2023), No. 63 / 488,719 (filed on March 6, 2023), No. 63 / 484, No. 004 (filed on February 9, 2023), No. 63 / 482,344 (filed on January 31, 2023), No. 63 / 515,918 (filed on July 27, 2023), No. 63 / 548,955 (filed on February 2024) This application claims priority to US Pat. Nos. 63 / 603,188 (filed Nov. 28, 2023), 63 / 505,433 (filed June 1, 2023), 63 / 516,684 (filed July 31, 2023), 63 / 627,346 (filed January 31, 2024), and 63 / 597,621 (filed Nov. 9, 2023), each of which is incorporated herein by reference in its entirety.

[0002] Field The present disclosure relates generally to organic or metal coordination compounds and formulations and their various applications as emitters, sensitizers, charge transporters or exciton transporters in devices such as organic light emitting diodes and related electronic devices and consumer products. [Background technology]

[0003] Optoelectronic devices that utilize organic materials are becoming increasingly desirable for a variety of reasons. Many of the materials used to fabricate such devices are relatively inexpensive, so organic optoelectronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as flexibility, may make them well suited 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, organic scintillators, and organic photodetectors. For OLEDs, organic materials may have performance advantages over traditional materials.

[0004] OLEDs utilize thin organic films that emit light when a voltage is applied across the device and are becoming an increasingly interesting technology for use in applications such as displays, lighting and backlighting.

[0005] One application of emissive molecules is full color displays. Industry standards for such displays require pixels adapted to emit specific colors, referred to as "saturated" colors. In particular, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. Conventional liquid crystal display emission from a white backlight is filtered with absorbing filters to produce red, green, and blue emission. Similar techniques can be used with OLEDs. White OLEDs can be either single-emissive layer (EML) devices or stack structures. Color can be measured using CIE coordinates, which are well known in the art. Summary of the Invention

[0006] In one aspect, the present disclosure provides a compound of formula (L A ) x (L B ) y (L C ) zwhere x is 1 or 2; y is 1 or 2; z is 0 or 1; and x+y+z=3; the first ligand L A is represented by formula I [ka] The ligand L B is represented by formula II [ka] and the ligand L C is a bidentate ligand, in which: Moiety B is a polycyclic fused ring system containing at least four rings, each ring of the polycyclic fused ring system being independently a 5-10 membered carbocyclic or heterocyclic ring; each of moieties C and D is independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5-10 membered carbocyclic or heterocyclic ring; X 1 ~X 4 and Z 1 ~Z 6 each is independently C or N; L 0 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, CRR', SiRR', GeRR', and combinations thereof; Y A BR N , N.R. N , P.R. N , O, S, Se, C═O, S═O, SO2, CRR′, SiRR′, and GeRR′; R A , R B , R C , and R D each independently represents from one substitution up to the maximum allowed substitution, or no substitution; Each R, R', R A , R B , R C , R D , and RN is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; and Any two substituents can be joined or fused to form a ring.

[0007] In another aspect, the present disclosure provides a compound of formula Ir(L A ) x (L B ) y (L C ) z The present invention provides a formulation comprising the compound of formula (I).

[0008] In yet another aspect, the present disclosure provides a compound of formula Ir(L A ) x (L B ) y (L C ) z An OLED having an organic layer comprising the compound of formula (I) is provided.

[0009] In yet another aspect, the present disclosure provides a compound of formula Ir(L A ) x (L B ) y (L C ) z The present invention provides a consumer product that includes an OLED having an organic layer that includes the compound of the present invention. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 shows an organic light emitting device.

[0011] [Diagram 2]FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] A. Terminology Unless otherwise stated, the following terms used herein are defined as follows.

[0013] As used herein, "top" means furthest from the substrate, while "bottom" means closest to the substrate. When a first layer is described as "disposed over" a second layer, the first layer is disposed further from the substrate. There may be other layers between the first and second layers, unless it is specified that the first layer is "in contact with" the second layer. For example, a cathode may be described as "disposed over" an anode, even though there are various organic layers in between.

[0014] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium, either in the form of a solution or suspension.

[0015] As used herein, and as generally understood by those skilled in the art, a first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IPs) are measured as negative energies relative to the vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (a less negative EA). In a conventional energy level diagram with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A "higher" HOMO or LUMO energy level appears closer to the top of such a diagram than a "lower" HOMO or LUMO energy level.

[0016] As used herein, as generally understood by those skilled in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Since work functions are generally measured as negative numbers relative to the vacuum level, this means that a "higher" work function is more negative. In a conventional energy level diagram with the vacuum level at the top, a "higher" work function is illustrated as being further away from the vacuum level in a downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

[0017] Layers, materials, regions, and devices may be described herein in relation to the color of light they emit. Generally, as used herein, a light-emitting region described as producing a particular color of light may include one or more light-emitting layers arranged relative to one another in a stack.

[0018] As used herein, a "NIR" layer, a "red" layer, a "green" layer, a "blue" layer, a "yellow" layer, a material, a region, or a device refers to a layer, a material, a region, or a device that emits light in the wavelength ranges of about 700-1500 nm, 580-700 nm, 500-600 nm, 400-500 nm, 540-600 nm, respectively, or that has the highest peak in its emission spectrum in the respective wavelength range. In some configurations, separate regions, layers, materials, or devices can provide separate "dark blue" and "light blue" emissions. As used herein, a "dark blue" emissive component refers to an emission that has a peak emission wavelength that is at least about 4 nm shorter than the peak emission wavelength of the "light blue" emissive component. Typically, the "light blue" emissive component has a peak emission wavelength in the range of about 465-500 nm and the "dark blue" emissive component has a peak emission wavelength in the range of about 400-470 nm, although these ranges can vary in some configurations.

[0019] In some configurations, a color changing layer is provided that converts, modifies, or shifts the color of light emitted by another layer to an emission having a different wavelength. Such color changing layers can be formulated to shift the wavelength of light emitted by another layer by a prescribed amount, as measured by the difference between the wavelength of the emitted light and the wavelength of the resulting light. Generally, there are two classes of color changing layers: color filters that modify the spectrum by removing undesirable wavelengths of light, and color changing layers that convert higher energy photons to lower energy. For example, a "red" color filter can be present to filter the input light to remove light having wavelengths outside the range of about 580-700 nm. A "color" component refers to a component that, when activated or used, produces or emits light having a particular color, as described above. For example, a "first light-emitting region of a first color" and a "second light-emitting region of a second color different from the first color" refer to two light-emitting regions that, when activated in a device, emit two different colors, as described above.

[0020] As used herein, light-emitting materials, layers, and regions may be distinguished from one another and from other structures based on the light that is initially generated by the material, layer, or region, as opposed to the light that is ultimately emitted by the same or a different structure. Typically, the initial generation of light is the result of a change in energy levels that results in the emission of a photon. For example, an organic light-emitting material may initially generate blue light, which may be converted to red or green light by color filters, quantum dots, or other structures, such that the complete light-emitting stack or subpixel emits red or green light. In this case, the initial light-emitting material, region, or layer may be referred to as the "blue" component, even if the subpixel is the "red" or "green" component.

[0021] In some instances, it may be preferable to describe the color of components of light-emitting regions, subpixels, color-changing layers, etc., in 1931 CIE coordinates. For example, a yellow light-emitting material may have multiple peak emission wavelengths, one within or near the edge of the "green" region as described above, and another within or near the edge of the "red" region. Thus, as used herein, each color term also corresponds to a shape in the 1931 CIE coordinate color space. The shape of the 1931 CIE color space is constructed by tracing the coordinates between two color points and any additional internal points. For example, the internal shape parameters for red, green, blue, and yellow may be defined as follows: [Table 1]

[0022] The terms "halo," "halogen," and "halide" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0023] The term "acyl" refers to a substituted carbonyl group (-C(O)-R s )

[0024] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s Or -C(O)-ORs ) group.

[0025] The term "ether" means -OR s Refers to the base.

[0026] The terms "sulfanyl" and "thioether" are used interchangeably, and include -SR s Refers to the base.

[0027] The term "selenyl" means -SeR s Refers to the base.

[0028] The term "sulfinyl" refers to -S(O)-R s Refers to the base.

[0029] The term "sulfonyl" means -SO2-R s Refers to the base.

[0030] The term "phosphino" refers to a group that contains at least one phosphorus atom bonded to the relevant structure. Common examples of phosphino groups include -P(R s )2 groups or -PO(R s ) 2 groups, but are not limited thereto. s may be the same or different.

[0031] The term "silyl" refers to a group that contains at least one silicon atom bonded to the relevant structure. A common example of a silyl group is -Si(R s )3 groups (in the formula, each R s may be the same or different), but are not limited to these.

[0032] The term "germyl" refers to a group that contains at least one germanium atom bonded to the relevant structure. A typical example of a germyl group is -Ge(R s )3 groups (in the formula, each R s may be the same or different), but are not limited to these.

[0033] The term "boryl" refers to a group that contains at least one boron atom bonded to the relevant structure. A common example of a boryl group is -B(R s )2 groups or their Lewis adducts -B(R s )3 groups (in the formula, R s may be the same or different), but are not limited to these.

[0034] In each of the above, R s can be hydrogen or a substituent selected from the group consisting of general substituents defined in this application. s is selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0035] The term "alkyl" refers to and includes both straight and branched chain alkyl groups having alkyl carbon atoms attached to the relevant structure. Preferred alkyl groups contain 1-15 carbon atoms, preferably 1-9 carbon atoms, and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. In addition, the alkyl groups may be further substituted.

[0036] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups having ring alkyl carbon atoms attached to the relevant structure. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. In addition, cycloalkyl groups may be further substituted.

[0037] The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. In addition, the heteroalkyl or heterocycloalkyl group may be further substituted.

[0038] The term "alkenyl" refers to and includes both straight-chain and branched-chain alkene groups. An alkenyl group is essentially an alkyl group containing at least one carbon-carbon double bond in the alkyl chain, with one carbon atom from the carbon-carbon double bond attached to the relevant structure. A cycloalkenyl group is essentially a cycloalkyl group containing at least one carbon-carbon double bond in the cycloalkyl ring. The term "heteroalkenyl" as used herein refers to an alkenyl 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, Ge, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing 2 to 15 carbon atoms. In addition, the alkenyl, cycloalkenyl, or heteroalkenyl groups may be further substituted.

[0039] The term "alkynyl" refers to and includes both straight-chain and branched-chain alkyne groups. Alkynyl groups are essentially alkyl groups that contain at least one carbon-carbon triple bond in the alkyl chain, with one carbon atom from the carbon-carbon triple bond attached to the relevant structure. Preferred alkynyl groups are those that contain 2 to 15 carbon atoms. In addition, the alkynyl groups may be further substituted.

[0040] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group having an alkyl carbon atom attached to the related structure. In addition, said aralkyl groups may be further substituted.

[0041] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, Se, N, P, B, Si, Ge, and Se, preferably O, S, N, or B. Heteroaromatic cyclic groups may be used interchangeably with heteroaryl. Preferred heteronon-aromatic cyclic groups are those containing 3-10 ring atoms, preferably 3-7 ring atoms, containing at least one heteroatom, and include cyclic amines such as morpholino, piperidino, pyrrolidino, and cyclic ethers / thioethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. In addition, the heterocyclic groups may be further substituted or fused.

[0042] The term "aryl" refers to and includes both monocyclic and polycyclic aromatic hydrocarbyl groups. Polycyclic rings can have two or more rings with two carbons shared between two adjacent rings (the rings being "fused"). Preferred aryl groups are those containing 6 to 30 carbon atoms, preferably those containing 6 to 24 carbon atoms, more preferably those containing 6 to 18 carbon atoms, and even more preferably those containing 6 to 12 carbon atoms. Particularly preferred are aryl groups having 6 carbons, 10 carbons, 12 carbons, 14 carbons, or 18 carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, pyrene, chrysene, perylene, and azulene, with phenyl, biphenyl, triphenyl, triphenylene, and naphthalene being preferred. In addition, the aryl group may be further substituted or fused to, for example, but not limited to, fluorene.

[0043] The term "heteroaryl" refers to and includes both monocyclic aromatic groups and polycyclic aromatic ring systems containing at least one heteroatom. Heteroatoms include, but are not limited to, O, S, Se, N, P, B, Si, Ge, and Se. In many instances, O, S, N, or B are the preferred heteroatoms. Heteromonocyclic aromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and said rings can have 1 to 6 heteroatoms. Heteropolycyclic ring systems can have two or more aromatic rings in which two atoms are common to two adjacent rings (the rings are "fused"), and at least one of the rings is heteroaryl. Heteropolycyclic aromatic ring systems can have 1 to 6 heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing 3 to 30 carbon atoms, with those containing 3 to 24 carbon atoms being preferred, those containing 3 to 18 carbon atoms being preferred, and those containing 3 to 12 carbon atoms being more preferred. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, o-phenyl- ... Xadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenophenodipyridine, azaborine, borazine, 5λ 2 ,9λ 2 -Diaza-13b-boranaphtho[2,3,4-de]anthracene, 5λ 2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene; preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 5λ 2 ,9λ 2 -Diaza-13b-boranaphtho[2,3,4-de]anthracene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene. In addition, the heteroaryl groups may be further substituted or fused.

[0044] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, benzimidazole, 5λ 2 ,9λ 2 -Diaza-13b-boranaphtho[2,3,4-de]anthracene, 5λ 2 Of particular interest are the -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene groups, as well as their respective aza analogues.

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

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

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

[0048] In some instances, even more preferred common substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof.

[0049] In yet other instances, the most preferred common substituents are selected from the group consisting of deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0050] The terms "substituted" and "substitution" refer to a substituent other than H attached to the relevant position (e.g., carbon or nitrogen). For example, R 1 If represents a single substitution, one R 1 must be other than H (i.e., a substitution). Similarly, R 1 If represents a disubstitution, R 1 must be other than H. Similarly, R 1 When R represents zero or no substitution, 1can be hydrogen at all available valences of the ring atoms, as in the case of carbon atoms in benzene and nitrogen atoms in pyrrole, or simply represent nothing in the case of ring atoms with fully filled valences (e.g., the nitrogen atom in pyridine). The maximum number of substitutions possible in a ring structure depends on the total number of available valences on the ring atoms.

[0051] As used herein, "combinations thereof" refers to one or more members of the applicable list being combined to form a known or chemically stable configuration that one of skill in the art can envision from the applicable list. For example, alkyl and deuterium can be combined to form a partially or fully deuterated alkyl group; halogen and alkyl can be combined to form a halogenated alkyl substituent; halogen, alkyl, and aryl can be combined to form a halogenated aryl alkyl. In one example, the term substituted includes combinations of 2-4 of the listed groups. In another example, the term substituted includes combinations of 2-3 groups. In yet another example, the term substituted includes combinations of 2 groups. Preferred combinations of substituents include those that contain up to 50 atoms that are not hydrogen or deuterium, or those that contain up to 40 atoms that are not hydrogen or deuterium, or those that contain up to 30 atoms that are not hydrogen or deuterium. In many examples, preferred combinations of substituents include up to 20 atoms that are not hydrogen or deuterium.

[0052] The designation "aza" in the fragments described herein, i.e., aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the CH groups in each aromatic ring can be replaced by a nitrogen atom, for example, but not by way of limitation, azatriphenylene includes both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of skill in the art can easily imagine other nitrogen analogs of the above-mentioned aza derivatives, and all such analogs are intended to be encompassed by the term described herein.

[0053] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, International Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. 2011 / 0037057, the contents of which are incorporated by reference in their entirety, describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Tetrahedron 2015, 71, 1425-30 (Ming Yan et al.) and Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65 (Atzrodt et al.), the contents of which are incorporated by reference in their entirety, which describe efficient routes for the deuteration of methylene hydrogens in benzylamines and the replacement of aromatic ring hydrogens with deuterium, respectively.

[0054] As used herein, any specifically recited substituent, such as but not limited to methyl, phenyl, pyridyl, etc., includes undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents, such as but not limited to alkyl, aryl, cycloalkyl, heteroaryl, etc., also include undeuterated, partially deuterated, and fully deuterated versions thereof. Unless otherwise specified, atoms in a chemical structure that do not have valences fully filled with H or D should be considered to include undeuterated, partially deuterated, and fully deuterated versions thereof. For example, the chemical structure [ka] is meant to include C6H6, C6D6, C6H3D3, and any other partially deuterated variants thereof. Some common basic groups that are partially or fully deuterated include, but are not limited to, CD3, CD2C(CH3)3, C(CD3)3, and C6D5.

[0055] When a molecular fragment is described as being a substituent or attached to another moiety, it is understood that the name may be described as being the fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or the entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, different ways of denoting the substituent or attached fragment are considered equivalent.

[0056] In some cases, pairs of substituents in a molecule can be optionally bonded or fused to form a ring. Preferred rings are 5- to 9-membered carbocyclic or heterocyclic rings, including both cases where the portion of the ring formed by the pair of substituents is saturated and cases where the portion of the ring formed by the pair of substituents is unsaturated. In still other cases, adjacent substituents in a pair can be optionally bonded or fused to form a ring. As used herein, "adjacent" means that the two related substituents can be on the same ring next to each other, or on two adjacent rings with the two nearest available substitutable positions, such as the 2- and 2'-positions in biphenyl, or the 1- and 8-positions in naphthalene.

[0057] B. Compounds of the Present Disclosure In one aspect, the present disclosure provides a compound of formula Ir(L A ) x (L B ) y (L C ) z wherein x is 1 or 2; y is 1 or 2; z is 0 or 1; and x+y+z=3; A is represented by formula I [ka] The ligand L B is represented by formula II [ka] and the ligand L Cis a bidentate ligand. In this compound, Moiety B is a polycyclic fused ring system containing at least four rings, each ring of the polycyclic fused ring system being independently a 5-10 membered carbocyclic or heterocyclic ring; each of moieties C and D is independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5-10 membered carbocyclic or heterocyclic ring; X 1 ~X 4 and Z 1 ~Z 6 each is independently C or N; L 0 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, CRR', SiRR', GeRR', and combinations thereof; Y A BR N , N.R. N , P.R. N , O, S, Se, C═O, S═O, SO2, CRR′, SiRR′, and GeRR′; R A , R B , R C , and R D each independently represents from one substitution up to the maximum allowed substitution, or no substitution; Each R, R', R A , R B , R C , R D , and R N are independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and Any two substituents can be linked or fused to form a ring to provide a compound of the formula:

[0058] In some embodiments, at least two R A The substituents may be linked to form a ring or at least one R A is not hydrogen.

[0059] In some embodiments, the compound is [ka] isn't it.

[0060] Z 1 -Z 2 join, Z 3 -Z 4 Bonds and Z 5 -Z 6 Although the bonds are shown as single bonds, it is understood that they may be any other bond (e.g., double bonds) necessary to form the applicable ring structure of moieties B, C, and D, respectively. This also applies to any other generalized ring or moiety structure disclosed herein.

[0061] In some embodiments, L A consists essentially of formula I. In some embodiments, L A has the structure of Formula I:

[0062] In some embodiments, L B consists essentially of formula II. In some embodiments, L B has the structure of Formula II.

[0063] In some embodiments of Formula I and Formula II, at least one of R, R′, R A , R B , R C , R D , and R N is 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 R C is partially or fully deuterated. In some embodiments, at least one R D is partially or fully deuterated. In some embodiments, R Nis partially or fully deuterated. In some embodiments, at least one R or R' is partially or fully deuterated.

[0064] In some embodiments, each of moieties C and D is independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- or 6-membered carbocyclic or heterocyclic ring. In some embodiments, each of moieties C and D is independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- or 6-membered aryl or heteroaryl ring.

[0065] In some embodiments, moiety B is a polycyclic fused ring system comprising at least four rings, each ring of the polycyclic fused ring system being independently a 5- or 6-membered carbocyclic or heterocyclic ring. In some embodiments, moiety B is a polycyclic fused ring system comprising at least four rings, each ring of the polycyclic fused ring system being independently a 5- or 6-membered aryl or heteroaryl ring. In some such embodiments, R B does not contain any EWG.

[0066] In some embodiments, Z 3 is N and L B When R is an unfused phenylpyridine ligand, C The substituents are not silyl or germyl. As used herein, unfused phenyl-pyridine means that neither the phenyl nor the pyridine moiety is cyclized with another ring. In some embodiments, Z 3 is N and moiety C contains a pyridine ring which coordinates to the metal, then R C The substituent is not silyl or germyl.

[0067] In some embodiments, each R, R′, R A , R B , R C , R D , and R Nis independently hydrogen or a substituent selected from the group consisting of preferred general substituents. In some embodiments, each R, R′, R A , R B , R C , R D , and R N is independently hydrogen or a substituent selected from the group consisting of the more preferred general substituents. In some embodiments, each R, R′, R A , R B , R C , R D , and R N is independently hydrogen or a substituent selected from the group consisting of even more preferred general substituents. In some embodiments, each R, R′, R A , R B , R C , R D , and R N is independently hydrogen or a substituent selected from the group consisting of the most preferred general substituents.

[0068] In some embodiments, the compound has the formula Ir(L A )2(L B In some embodiments, the compound has the formula Ir(L A )(L B In some embodiments, the compound has the formula Ir(L A )(L B )(L C ).

[0069] In some embodiments, moiety B is a polycyclic fused ring system containing exactly four rings. In some such embodiments, the moiety does not contain any EWGs.

[0070] In some embodiments, moiety B is a polycyclic fused ring system containing at least five rings, and each ring of the polycyclic fused ring system is independently a 5-10 membered carbocyclic or heterocyclic ring. In some embodiments, moiety B is a polycyclic fused ring system containing exactly five rings, and each ring of the polycyclic fused ring system is independently a 5-10 membered carbocyclic or heterocyclic ring.

[0071] In some embodiments, moiety B is a polycyclic fused ring system containing at least six rings, where each ring of the polycyclic fused ring system is independently a 5-10 membered carbocyclic or heterocyclic ring. In some embodiments, moiety B is a polycyclic fused ring system containing exactly six rings, where each ring of the polycyclic fused ring system is independently a 5-10 membered carbocyclic or heterocyclic ring.

[0072] In some embodiments, moiety B contains exactly one 5-membered ring and the remaining rings are 6-membered rings. In some such embodiments, each of the exactly one 5-membered rings is a heterocycle.

[0073] In some embodiments, moiety B comprises exactly two 5-membered rings and the remaining ring is a 6-membered ring. In some embodiments, each of the exactly two 5-membered rings is a heterocyclic ring.

[0074] In some embodiments, each of the two five-membered rings is a furan ring or a thiophene ring. In some embodiments, each of the two five-membered rings is a furan ring. In some embodiments, each of the two five-membered rings is a thiophene ring. In some embodiments, one of the five-membered rings is a furan ring and the other five-membered ring is a thiophene ring.

[0075] In some embodiments, at least one ring atom is different in the two five-membered rings. In some embodiments, moiety B contains at least one hetero ring atom other than O and S. In some embodiments, moiety B contains at least one Si as a ring atom.

[0076] In some embodiments, moiety B comprises at least one N ring atom. In some embodiments, moiety B comprises exactly one N ring atom. In some embodiments, moiety B comprises exactly two N ring atoms. In some embodiments, moiety B comprises exactly three N ring atoms. In some embodiments, moiety B comprises exactly four N ring atoms.

[0077] In some embodiments, the moiety B does not include an N ring atom.

[0078] In some embodiments, moiety B contains up to 1 N ring atom per ring. In some embodiments, moiety B contains up to 2 N ring atoms per ring. In some embodiments, moiety B contains up to 3 N ring atoms per ring. In some embodiments, moiety B contains up to 4 N ring atoms per ring.

[0079] In some embodiments, exactly one ring of moiety B has an N ring atom and that ring is fused to exactly one other ring of moiety B. In some embodiments, exactly one ring of moiety B has an N ring atom and that ring is fused to exactly two other rings of moiety B. In some embodiments, exactly one ring of moiety B has an N ring atom and that ring is fused to exactly three other rings of moiety B.

[0080] In some embodiments, moiety B comprises moiety B1 and moiety B2, and moiety B1 is Z 1 and Z 2 wherein moiety B2 is fused to moiety B1, and each of moieties B1 and B2 is independently a monocyclic ring or a polycyclic fused ring system, and each ring of the monocyclic ring or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring.

[0081] In some embodiments, each of moieties B1 and B2 is independently selected 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, benzoseleno phene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole derived carbene, aza-benzimidazole derived carbene, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

[0082] In some embodiments, moiety B1 is dibenzofuran and moiety B2 is benzene, naphthalene, or benzofuran. In some such embodiments, moiety B2 comprises benzofuran and the benzo ring is Z 1 -Z 2 Includes.

[0083] In some embodiments, the moiety B1 is benzofuran and the moiety B2 is naphthalene, anthracene, phenanthrene, or dibenzofuran. In some embodiments, the moiety B2 comprises dibenzofuran, one benzo of the dibenzofuran being Z 1 -Z 2 Includes.

[0084] In some embodiments, at least one of moieties B, C, and D may independently be a polycyclic fused ring structure. In some embodiments, at least one of moieties B, C, and D may independently be a polycyclic fused ring structure comprising at least two fused rings. In some embodiments, the polycyclic fused ring structure has one six-membered ring and one five-membered ring. In some such embodiments, either the five-membered ring or the six-membered ring may be coordinated to the Ir atom. In some embodiments, the polycyclic fused ring structure has two six-membered rings. In some embodiments, at least one of moieties B, C, and D may independently be selected from the group consisting of benzofuran, benzothiophene, benzoselenophene, naphthalene, and aza variants thereof.

[0085] In some embodiments, at least one of moieties B, C, and D can be a polycyclic fused ring structure comprising at least three fused rings. In some embodiments, the polycyclic fused ring structure has two six-membered rings and one five-membered ring. In some such embodiments, the five-membered ring is fused to a ring coordinated to the Ir atom, and a second six-membered ring is fused to the five-membered ring. In some embodiments, at least one of moieties B, C, and D can be independently selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and azavariants thereof. In some such embodiments, at least one of moieties B, C, and D can be further independently substituted at the ortho or meta positions of the O, S, or Se atom with a substituent independently selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the azavariant contains exactly one N atom at the 6 position (ortho to O, S, or Se) and has a substituent at the 7 position (meta to O, S, or Se).

[0086] In some embodiments, at least one of moieties B, C, and D can independently be a polycyclic fused ring structure comprising at least four fused rings. In some embodiments, the polycyclic fused ring structure comprises three six-membered rings and one five-membered ring. In some such embodiments, the five-membered ring is fused to a ring coordinated to the Ir atom, a second six-membered ring is fused to the five-membered ring, and a third six-membered ring is fused to the second six-membered ring. In some such embodiments, the third six-membered ring is further substituted with a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0087] In some embodiments, at least one of moieties B, C, and D may independently be a polycyclic fused ring structure comprising at least five fused rings. In some embodiments, the polycyclic fused ring structure comprises four six-membered rings and one five-membered ring, or three six-membered rings and two five-membered rings. In some embodiments comprising two five-membered rings, the five-membered rings are fused together. In some embodiments comprising two five-membered rings, the five-membered rings are separated by at least one six-membered ring. In some embodiments comprising one five-membered ring, the five-membered ring is fused to a ring coordinated to the Ir atom, a second six-membered ring is fused to the five-membered ring, a third six-membered ring is fused to the second six-membered ring, and a fourth six-membered ring is fused to the third six-membered ring.

[0088] In some embodiments, at least one of moieties B, C, and D may independently be an aza type of the polycyclic fused ring described above. In some such embodiments, at least one of moieties B, C, and D may independently contain exactly one aza N atom. In some such embodiments, at least one of moieties B, C, and D may contain exactly two aza N atoms, which may be in one ring or in two different rings. In some such embodiments, the ring with the aza N atom is separated from the Ir atom by at least two other rings. In some such embodiments, the ring with the aza N atom is separated from the Ir atom by at least three other rings. In some such embodiments, each of the ortho positions of the aza N atom is substituted.

[0089] In some embodiments, Z 1 and Z 2 is C. In some embodiments, Z 1 is C and Z 2 is N.

[0090] In some embodiments, X 1 ~X 4 Each of is C.

[0091] In some embodiments, X 1 ~X 4 At least one of X is N. In some embodiments, 1 ~X 4 Exactly one of is N.

[0092] In some embodiments, X 1 ~X 4 At least two of X are N. In some embodiments, 1 ~X 4 Exactly two of are N.

[0093] In some embodiments, each of moieties C and D is independently selected from the group consisting of the list of cyclic moieties defined herein. In some embodiments, the azavariant contains one N on the benzo ring. In some embodiments, the lone N on the benzo ring is bonded to an Ir atom.

[0094] In some embodiments, moiety C is a monocyclic ring. In some embodiments, moiety C 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 C is pyridine or pyrimidine. In some embodiments, moiety C is pyridine. In some embodiments, moiety C is pyrimidine.

[0095] In some embodiments, moiety C is a polycyclic fused ring system. In some embodiments, moiety C is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, moiety C is quinoline or isoquinoline.

[0096] In some embodiments, moiety D is a monocyclic ring. In some embodiments, moiety D 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 D is benzene.

[0097] In some embodiments, moiety D is a polycyclic fused ring system. In some embodiments, moiety D is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, moiety D is naphthalene.

[0098] In some embodiments, Z 3 is N and Z 4 is C. In some embodiments, Z 3 is the carbene carbon, and Z 4 is N.

[0099] In some embodiments, Z 5 and Z 6 is C. In some embodiments, Z 5 is N and Z 6 is C.

[0100] In some embodiments, L 0 is a direct bond.

[0101] In some embodiments, L0 is O, S, or Se. In some embodiments, L 0 is BR, NR, or PR. In some embodiments, L 0 is P(O)R, C=O, C=S, C=Se, C=NR, C=CRR', S=O, or SO2. In some embodiments, L 0 is BRR', CRR', SiRR', or GeRR'.

[0102] In some embodiments, Y A is O, S, or Se. In some embodiments, Y A BR N , N.R. N , or PR N In some embodiments, Y A is NR N In some embodiments, Y A is C=O, S=O, or SO2. In some embodiments, Y A is CRR', SiRR', or GeRR'.

[0103] In some embodiments, the compound comprises an electron withdrawing group. In some embodiments, the electron withdrawing group has a Hammett constant greater than 0. In some embodiments, the electron withdrawing group has a Hammett constant greater than or equal to 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1.

[0104] In some embodiments, the first ligand L A The following structures are listed in EWG1: 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 Rk2 , substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridoxine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, [ka] (In the formula, each R k1 represents one substitution up to the maximum allowed substitution, or no substitution; Y G BR e , N.R. e , P.R. e , O, S, Se, C=O, S=O, SO2, CR e R f , SiR e R f , and GeR e R f selected from the group consisting of: R k1 , R k2 , R k3 , R e , and R f Each of the formulas contains an electron withdrawing group selected from the group consisting of: is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein.

[0105] In some embodiments, the first ligand L A The following EWG2 listed structures: [ka] [ka] [ka] The electron withdrawing group is selected from the group consisting of:

[0106] In some embodiments, the first ligand L A The following EWG3 listed structures: [ka] The electron withdrawing group is selected from the group consisting of:

[0107] In some embodiments, the first ligand L A The following EWG4 lists the structures: [ka] The electron withdrawing group is selected from the group consisting of:

[0108] In some embodiments, the first ligand L A The following Pi-EWG lists structures: CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, + N(R k2 )3, BR k2 R k3, substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridazine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketones, carboxylic acids, esters, nitriles, isonitriles, sulfinyls, sulfonyls, partially and fully fluorinated aryls, partially and fully fluorinated heteroaryls, cyano-containing aryls, cyano-containing heteroaryls, isocyanates, [ka] wherein the variables are the same as defined above.

[0109] In some embodiments, at least one R A is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0110] In some embodiments, at least one R B is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R Bis or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0111] In some embodiments, at least one R or R' is or comprises an electron withdrawing group from the EWG1 list, as defined herein. In some embodiments, at least one R or R' is or comprises an electron withdrawing group from the EWG2 list, as defined herein. In some embodiments, at least one R or R' is or comprises an electron withdrawing group from the EWG3 list, as defined herein. In some embodiments, at least one R or R' is or comprises an electron withdrawing group from the EWG4 list, as defined herein. In some embodiments, at least one R or R' is or comprises an electron withdrawing group from the Pi-EWG list, as defined herein.

[0112] In some embodiments, R N is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, R N is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, R N is or includes an electron withdrawing group from the EWG3 list as defined herein. N is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, R N is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0113] In some embodiments, at least one R A is not hydrogen. In some embodiments, X 1 R A is not hydrogen. In some embodiments, X 2 R A is not hydrogen. In some embodiments, X 3 R A is not hydrogen. In some embodiments, X 4 R A is not hydrogen.

[0114] In some embodiments, at least one R A is not hydrogen or deuterium. In some embodiments, at least two R A is not independently hydrogen or deuterium. 1 R A is not hydrogen or deuterium. 2 R A is not hydrogen or deuterium. 3 R A is not hydrogen or deuterium. 4 R A is not hydrogen or deuterium.

[0115] In some embodiments, at least one R A contains at least one C atom. In some embodiments, at least one R A contains at least two C atoms. In some embodiments, at least one R A contains at least three C atoms. In some embodiments, at least one R A contains at least four C atoms.

[0116] In some embodiments, X 1 R A contains at least one C atom. In some embodiments, X 2 R Acontains at least one C atom. In some embodiments, X 3 R A contains at least one C atom. In some embodiments, X 4 R A contains at least one C atom.

[0117] In some embodiments, at least one R A In some embodiments, at least two R A includes substituents independently selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0118] In some embodiments, X 1 R A In some embodiments, X includes a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof. 2 R A In some embodiments, X includes a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof. 3 R A In some embodiments, X includes a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof. 4 R A includes substituents selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0119] In some embodiments, exactly one R A is not H. In some embodiments, exactly one R A is not H or D. In some embodiments, exactly one R Acontains at least one C atom. In some embodiments, at least one R A is a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. A is a substituent independently selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof.

[0120] In some embodiments, two adjacent R A are bonded or fused to form a moiety A1, which is a monocyclic ring or a polycyclic fused ring system, each ring of which is independently a 5- to 10-membered carbocyclic or heterocyclic ring. Each is independently a 5- to 10-membered carbocyclic or heterocyclic ring.

[0121] In some embodiments, the moiety A1 is X 1 -X 2 In some embodiments, the moiety A1 is condensed with X 2 -X 3 In some embodiments, the moiety A1 is condensed with X 3 -X 4 is condensed with

[0122] In some embodiments, the moiety A1 is selected from the group consisting of the list of cyclic moieties defined herein.

[0123] In some embodiments, the moiety A1 is a monocyclic ring. In some embodiments, the moiety A1 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, the moiety A1 is benzene or pyridine. In some embodiments, the moiety A1 is pyridine. In some embodiments, the moiety A1 is pyridine.

[0124] In some embodiments, the moiety A1 is a polycyclic fused ring system. In some embodiments, the moiety A1 is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, the moiety A1 is naphthalene.

[0125] In some embodiments, the moiety A1 comprises at least one non-aromatic ring. In some embodiments, the moiety A1 is a non-aromatic ring.

[0126] In some embodiments, the moiety A1 contains only carbon ring atoms (ie, is carbocyclic).

[0127] In some embodiments, the moiety A1 contains exactly one heteroatom. In some embodiments, the moiety A1 contains exactly two heteroatoms. In some embodiments, the moiety A1 contains exactly three heteroatoms.

[0128] In some embodiments, the moiety A1 comprises at least one heterocyclic ring. In some embodiments, the heterocyclic ring has one N atom. In some embodiments, the heterocyclic ring has two N atoms.

[0129] In some embodiments, the moiety A1 comprises at least one 5-membered ring. In some embodiments, the moiety A1 comprises at least one furan ring. In some embodiments, the moiety A1 comprises at least one electron-withdrawing group. In some embodiments, the moiety A1 is substituted with at least one electron-withdrawing group (e.g., EWG1 list, EWG2 list, EWG3 list, EWG4 list, Pi-EWG list).

[0130] In some embodiments, X 1 and X 2 R A are combined to form the moiety A1, and X 3 and X 4 R A are linked to form a moiety A2, where the moiety A2 is selected from the group consisting of the list of cyclic moieties defined herein.

[0131] In some embodiments, moiety A1 is a carbocyclic ring or system. In some embodiments, moiety A2 comprises at least one heterocyclic ring. In some such embodiments, the heterocyclic ring has one N atom. In some such embodiments, the heterocyclic ring has two N atoms. In some embodiments, moiety A2 comprises at least one five-membered ring. In some embodiments, moiety A2 comprises at least one furan ring. In some embodiments, moiety A2 comprises at least one electron-withdrawing group.

[0132] In some embodiments, at least one R B is not hydrogen.

[0133] In some embodiments, at least one R B is not hydrogen or deuterium. In some embodiments, at least two R B are not independently hydrogen or deuterium.

[0134] In some embodiments, at least one R B contains at least one C atom. In some embodiments, at least one R B contains at least two C atoms. In some embodiments, at least one R B contains at least three C atoms. In some embodiments, at least one R B contains at least four C atoms.

[0135] In some embodiments, at least one R B In some embodiments, at least two R B includes substituents independently selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0136] In some embodiments, each R attached to the distal ring of moiety B is B is independently H or D. In some embodiments, each R attached to the distal ring of moiety B is B is H. In some embodiments, each R attached to the distal ring of moiety B B are independently H or D, with at least one being D. As used herein, "distal" refers to the ring that, when traveling through moiety B, is furthest from the ring coordinated to the Ir atom.

[0137] In some embodiments, Y A is NR N , B.R. N , or PR NIn some embodiments, Y A is NR N It is.

[0138] In some embodiments, R N is not hydrogen.

[0139] In some embodiments, R N is not hydrogen or deuterium.

[0140] In some embodiments, R N contains at least one C atom. In some embodiments, R N contains at least two C atoms. In some embodiments, R N contains at least 3 C atoms. In some embodiments, R N contains at least four C atoms.

[0141] In some embodiments, R N includes substituents selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0142] In some embodiments, R N is represented by the structure of formula III [ka] (In the formula, ring F is a 5- to 10-membered carbocyclic or heterocyclic ring; R F represents mono- to tri-substituted or unsubstituted; Each R 1’ , R 2’ , and R F is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and R 1’ or R 2’ at least one of which is not hydrogen or deuterium.

[0143] In some embodiments, ring F is a 5- or 6-membered carbocyclic or heterocyclic ring. In some embodiments, ring F is a 5- or 6-membered aryl or heteroaryl ring.

[0144] In some embodiments, R 1’ Also 2’ is also not hydrogen or deuterium. 1’ or R 2’ At least one of is or includes aryl or heteroaryl.

[0145] In some embodiments, R 1’ and R 2’ Each of R is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, and combinations thereof. 1’ and R 2’ are the same. In some embodiments, R 1’ and R 2’ is different.

[0146] In some embodiments, R 1’ and R 2’ Each of independently contains at least one carbon atom. In some embodiments, R 1’ and R 2’ Each of independently contains at least two carbon atoms. In some embodiments, R 1’ and R 2’ Each of R independently contains at least 3 carbon atoms. 1’ and R 2’ Each of independently contains at least 4 carbon atoms. In some embodiments, R 1’ and R 2’ Each independently contains at least 5 carbon atoms.

[0147] In some embodiments, at least one R F is not hydrogen or deuterium.

[0148] In some embodiments, at least one RF is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, and combinations thereof. In some embodiments, at least one R F is or includes aryl or heteroaryl.

[0149] In some embodiments, ring F is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.

[0150] In some embodiments, R N is a structure of formula IV [ka] (In the formula, X 1a , X 2a , and X 3a each of is independently C or N.

[0151] In some embodiments, at least one R F is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, and combinations thereof. In some embodiments, at least one R F is alkyl. In some embodiments, at least one R F is aryl or heteroaryl. In some embodiments, at least one R F is silyl. In some embodiments, at least one R F is germyl.

[0152] In some embodiments, X 1a R bound to F is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, and combinations thereof. 2a R bound toF is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, and combinations thereof. 3a R bound to F is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, and combinations thereof.

[0153] In some embodiments, X 1a R bound to F is alkyl. In some embodiments, X 1a R bound to F is aryl or heteroaryl. In some embodiments, X 1a R bound to F is a substituted or unsubstituted phenyl or biphenyl. In some embodiments, X 1a R bound to F is silyl. In some embodiments, X 1a R bound to F is germyl.

[0154] In some embodiments, X 2a R bound to F is alkyl. In some embodiments, X 2a R bound to F is aryl or heteroaryl. In some embodiments, X 2a R bound to F is a substituted or unsubstituted phenyl or biphenyl. In some embodiments, X 2a R bound to F is silyl. In some embodiments, X 2a R bound to F is germyl.

[0155] In some embodiments, X 3a R bound to F is alkyl. In some embodiments, X 3a R bound to Fis aryl or heteroaryl. In some embodiments, X 3a R bound to F is a substituted or unsubstituted phenyl or biphenyl. In some embodiments, X 3a R bound to F is silyl. In some embodiments, X 3a R bound to F is germyl.

[0156] In some embodiments, at least one R F is or includes a substituted or unsubstituted phenyl or biphenyl.

[0157] In some embodiments, X 1a R bonded to F is or includes a substituted or unsubstituted phenyl or biphenyl. In some embodiments, X 2a R bonded to F is or includes a substituted or unsubstituted phenyl or biphenyl. In some embodiments, X 3a R bonded to F is or includes a substituted or unsubstituted phenyl or biphenyl.

[0158] In some embodiments, X 1a , X 2a , and X 3a Each of X is C. In some embodiments, 1a , X 2a , and X 3a At least one of X is N. In some embodiments, 1a , X 2a , and X 3a Exactly one of is N.

[0159] In some embodiments, L B comprises an electron withdrawing group from the EWG1 list as defined herein. B comprises an electron withdrawing group from the EWG2 list as defined herein.B comprises an electron withdrawing group from the EWG3 list as defined herein. B comprises an electron withdrawing group from the EWG4 list as defined herein. B contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0160] In some embodiments, at least one R C is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R C is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R C is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R C is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R C is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0161] In some embodiments, at least one R D is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R D is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R D is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R D is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R D is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0162] In some embodiments, at least one R or R' is or comprises an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R or R' is or comprises an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R or R' is or comprises an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R or R' is or comprises an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R or R' is or comprises an electron withdrawing group from the Pi-EWG list as defined herein.

[0163] In some embodiments, at least one R C is not hydrogen. In some embodiments, at least one R C is not hydrogen or deuterium. In some embodiments, at least two R C are not independently hydrogen or deuterium.

[0164] In some embodiments, at least one R C contains at least one C atom. In some embodiments, at least one R C contains at least two C atoms. In some embodiments, at least one R C contains at least three C atoms. In some embodiments, at least one R C contains at least four C atoms.

[0165] In some embodiments, at least one R C In some embodiments, at least two R C includes substituents independently selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0166] In some embodiments, at least one R D is not hydrogen. In some embodiments, at least one R D is not hydrogen or deuterium. In some embodiments, at least two R D are not independently hydrogen or deuterium.

[0167] In some embodiments, at least one R D contains at least one C atom. In some embodiments, at least one R D contains at least two C atoms. In some embodiments, at least one R D contains at least three C atoms. In some embodiments, at least one R D contains at least four C atoms.

[0168] In some embodiments, at least one R D In some embodiments, at least two R D includes substituents independently selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

[0169] In some embodiments, at least one R D comprises a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and electron withdrawing groups of the EWG1 list as defined herein. In some embodiments, at least two R D R independently comprises a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and electron-withdrawing groups of the EWG1 list defined herein. In some embodiments, at least three R Dcomprises substituents independently selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and electron-withdrawing groups of the EWG1 list as defined herein.

[0170] In some embodiments, Z 5 and Z 6 The ring containing R is a six-membered ring and is para to the bond to the moiety C. D (R Dp ) contains at least one C atom.

[0171] In some embodiments, R Dp comprises a moiety selected from the group consisting of alkyl, partially or fully deuterated alkyl, cycloalkyl, partially or fully deuterated cycloalkyl, ether, and electron withdrawing groups.

[0172] In some embodiments, R Dp comprises a moiety selected from the group consisting of alkyl, partially or fully deuterated alkyl, cycloalkyl, partially or fully deuterated cycloalkyl, and ether.

[0173] In some embodiments, R Dp comprises a moiety selected from the group consisting of CH3, CD3, isopropyl, t-butyl, partially or fully deuterated isopropyl, partially or fully deuterated neopentyl, cyclohexane, partially or fully deuterated cyclohexane, OCH3, and F.

[0174] In some embodiments, R Dp comprises a moiety selected from the group consisting of CH3, CD3, t-butyl, fully deuterated t-butyl, and F.

[0175] In some embodiments, R Dp comprises an electron withdrawing group. In some embodiments, R Dp is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, R Dpis or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, R Dp is or includes an electron withdrawing group from the EWG3 list as defined herein. Dp is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, R Dp is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0176] In some embodiments, R Dp is F, CH3, CD3, or carbazole.

[0177] In some embodiments, R Dp is F. In some embodiments, R Dp is F and the compound contains at least one electron-withdrawing group other than F.

[0178] In some embodiments, R Dp is CN or CD3.

[0179] In some embodiments, R Dp is a partially or fully fluorinated alkyl.

[0180] In some embodiments, R Dp comprises a silyl group or a germyl group. In some embodiments, R Dp is selected from the group consisting of R2 through R130, which have the structures defined in List 1 below. [ka] [ka] [ka]

[0181] In some embodiments, Z3 or Z 6 is C and Z 3 or Z 6 The other of Z is N. In some embodiments, Z 3 is N and Z 6 is C.

[0182] In some embodiments, L B is represented by formula IIA: [ka] (In the formula, X 1 ~X 4 at least one of is N.

[0183] In some embodiments of formula IIA, X 1 ~X 4 Exactly one of is N.

[0184] In some embodiments of formula IIA, X 1 is N. In some embodiments of formula IIA, X 2 is N. In some embodiments of formula IIA, X 3 is N. In some embodiments of formula IIA, X 4 is N.

[0185] In some embodiments of Formula IIA, R C At least one of is a tertiary alkyl, silyl or germyl.

[0186] In some embodiments of Formula IIA, R C At least one of is a tertiary alkyl.

[0187] In certain embodiments of formula IIA, X 3 is C and R is bonded to it. C is tertiary alkyl, silyl or germyl.

[0188] In some embodiments of formula IIA, X 1 ~X 3 is C and X4 is N and X 3 R bound to C is tertiary alkyl, silyl or germyl.

[0189] In some embodiments of formula IIA, X 1 ~X 3 is C and X 4 is N and X 2 R bound to C is tertiary alkyl, silyl or germyl.

[0190] In some embodiments of formula IIA, at least one of R D is tertiary alkyl, silyl, or germyl.In some embodiments of formula IIA, at least one of R D is tert-butyl.

[0191] In some embodiments of formula IIA, at least one pair of R C , a pair of R D , or one R C and one R D are bonded or condensed to form a ring.

[0192] In some embodiments, L C comprises an electron withdrawing group from the EWG1 list as defined herein. 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. C comprises an electron withdrawing group from the EWG4 list as defined herein. C contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0193] In some embodiments, the structure of Formula I [ka] is the following structure in Listing 2: [ka] [ka] [ka] [ka] [ka] (In the formula, X 5 ~X 12 each is independently C or N; Each Y B , Y B’ , Y C , and Y D is an independent BR e , N.R. e , P.R. e , O, S, Se, C=O, S=O, SO2, CR e R f , SiR e R f , and GeR e R f selected from the group consisting of; R AA represents one substitution up to the maximum possible number of substitutions, or no substitutions; Each R e , R f , and R AA are independently selected from the group consisting of hydrogen or the general substituents defined herein; The remaining variables are the same as defined previously; Any two substituents may be joined or fused to form a ring; * indicates the position of attachment to moiety B, --- indicates a bond to a metal.

[0194] Ligand L A In some embodiments, where R is selected from List 2, AAis a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfanyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. AA is a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof.

[0195] In some embodiments having portions of List 2, Y A is NR N In some embodiments, Y B , Y C , or Y D At least one of Y is O. B , Y C , or Y D At least one of Y is C=O. B , Y C , or Y D At least one of the following is NR e In some such embodiments, R e is R as described herein. N In some embodiments, Y B , Y C , or Y D At least one of Y is BR. B , Y C , or Y DAt least one of the following is NR, and Y B , Y C , or Y D At least one of the others is BR.

[0196] In some embodiments having portions of List 2, the presence of X 1 ~X 12 At least one of X is N. 1 ~X 12 At least two of X are N. 1 ~X 12 Each of is C.

[0197] In some embodiments, the structure of Formula I [ka] is the following structure in Listing 3: [ka] [ka] [ka] [ka] (In the formula, X 50 ~X 63 each is independently C or N; Each Y E , Y F , Y G , and Y H is an independent BR e , N.R. e , P.R. e , O, S, Se, C=O, S=O, SO2, CR e R f , SiR e R f , and GeR e R f selected from the group consisting of; RBB represents one substitution up to the maximum possible number of substitutions, or no substitutions; Each R e , R f , and R BB are independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; Any two substituents may be joined or fused to form a ring; # indicates the position of attachment to moiety A, --- indicates a bond to a metal.

[0198] Ligand L A In some embodiments, where R is selected from List 3, BB is a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. BB is a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof.

[0199] In some embodiments of Listing 2 and Listing 3, moiety B is X 53 In some such embodiments, X 50 is carbon and is coordinated to the Ir atom.

[0200] In some embodiments, the ligand L A is the following structure in Listing 4: [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, X5~X 30 each is independently C or N; Y B and Y C Each of the following is independently e , N.R. e , P.R. e , O, S, Se, C=O, S=O, SO2, CR e R f , SiR e R f , and GeR e R f selected from the group consisting of; R A1 represents one substitution up to the maximum possible number of substitutions; Each R A , R B1 , R B2 , and R B3independently represent one substitution up to the maximum possible number of substitutions, or no substitution; Each R e , R f , R A , R A1 , R B1 , R B2 , and R B3 are independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; The remaining variables are the same as defined previously; If present, at least one R A1 is not hydrogen; and Any two adjacent substituents may be fused or linked to form a ring or to form a multidentate ligand.

[0201] Ligand L A In some embodiments, R is selected from List 4. A , R A1 , R B1 , R B2 , or R B3 At least one of R is independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. A or R A1is a substituent independently selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. A , R A1 , R B1 , R B2 , or R B3 At least two of R are independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. A or R A1 is a substituent independently selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof.

[0202] Ligand L A In some embodiments, R is selected from List 4. e , R f , R A , R A1 , R B1 , R B2 , or R B3At least one of R is partially or fully deuterated. A is partially or fully deuterated. In some embodiments, at least one R A1 is partially or fully deuterated. In some embodiments, at least one R B1 is partially or fully deuterated. In some embodiments, at least one R B2 is partially or fully deuterated. In some embodiments, at least one R B3 is partially or fully deuterated. In some embodiments, at least one R e or R f is partially or fully deuterated.

[0203] Ligand L A In some embodiments, where R is selected from List 4, A is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0204] Ligand L A In some embodiments, where R is selected from List 4, A1 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A1is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A1 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A1 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A1 is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0205] Ligand L A In some embodiments, where R is selected from List 4, B1 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B1 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B1 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B1 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B1 is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0206] Ligand L A In some embodiments, where R is selected from List 4, B2 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B2 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B2is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B2 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B2 is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0207] Ligand L A In some embodiments, where R is selected from List 4, B3 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B3 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B3 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B3 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B3 is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0208] In some embodiments, the ligand L A is the following structure in Listing 5: [ka] [ka] [ka] [ka] [ka] (In the formula, Y B and Y C Each of the following is independently e , N.R. e , P.R. e , O, S, Se, C=O, S=O, SO2, CR e R f , SiR e R f , and GeR e R f selected from the group consisting of; R A1 represents one substitution up to the maximum possible number of substitutions; Each R A , R A1 , R B1 , R B2 and R B3 independently represent one substitution up to the maximum possible number of substitutions, or no substitution; Each R e , R f , R A , R A1 , R B1 , R B2 , R B3 , R e , and R f are independently selected from the group consisting of hydrogen or the general substituents defined herein; At least one R A1 is not hydrogen; The remaining variables are the same as previously defined; and Any two adjacent substituents may be fused or linked to form a ring or to form a multidentate ligand.

[0209] Ligand L A In some embodiments, R is selected from List 5. A , R A1 , R B1 , R B2 , or R B3At least one of R is independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. A or R A1 is a substituent independently selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. A , R A1 , R B1 , R B2 , or R B3 At least two of R are independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. A or R A1is a substituent independently selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof.

[0210] Ligand L A In some embodiments, R is selected from List 5. e , R f , R A , R A1 , R B1 , R B2 , or R B3 At least one of R is partially or fully deuterated. A is partially or fully deuterated. In some embodiments, at least one R A1 is partially or fully deuterated. In some embodiments, at least one R B1 is partially or fully deuterated. In some embodiments, at least one R B2 is partially or fully deuterated. In some embodiments, at least one R B3 is partially or fully deuterated. In some embodiments, at least one R e or R f is partially or fully deuterated.

[0211] Ligand L A In some embodiments, where R is selected from List 5, A is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one RA is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0212] Ligand L A In some embodiments, where R is selected from List 5, A1 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A1 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A1 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R A1 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A1 is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0213] Ligand L A In some embodiments, where R is selected from List 5, B1 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B1 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B1 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B1is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B1 is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0214] Ligand L A In some embodiments, where R is selected from List 5, B2 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B2 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B2 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B2 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B2 is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0215] Ligand L A In some embodiments, where R is selected from List 5, B3 is or includes an electron withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B3 is or includes an electron withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B3 is or includes an electron withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B3 is or includes an electron withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B3 is or contains an electron withdrawing group from the Pi-EWG list as defined herein.

[0216] In some embodiments, the ligand L A L Ai (R J )(R K )(R L )(Y M ), L Ai’ (R J )(R K )(R L )(Y M )(Y N ), L A’i’’ (R J )(R K )(R L )(Y M ), L A’i’’’ (R J )(R K )(R L )(Y M )(Y N ), In the formula, i is an integer of 1 to 21, i' is an integer of 22 to 64, i'' is an integer of 1 to 38, and i''' is an integer of 39 to 78; R J , R K , and R L each is independently selected from R1 to R411; R K’ is selected from R2 to R411; and Y M and Y N each is independently selected from Y1-Y50; In the formula, L A 1-(R1)(R1)(R1)(Y1)~L A Each of 64-(R411)(R411)(R411)(Y50)(Y50) has the structure defined in List 6 below: [ka] [ka] [ka] [ka] [ka] [ka] [ka] wherein L A’ 1-(R1)(R2)(R1)(Y1)~L A’ Each of 78-(R411)(R411)(R411)(Y50)(Y50) has the structure defined in List 7 below: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] wherein R1 to R411 have the structures shown in List 8 below: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] wherein Y1 to Y50 have the structures shown in List 9 below: [ka] [ka] has.

[0217] In some embodiments, L B would be the following structure in Listing 10: [ka] [ka] is selected from the group consisting of L C Listing 10 and [ka] is selected from the group consisting of During the ceremony, T is selected from the group consisting of B, Al, Ga, and In; K 1’ is a single bond, O, S, NR e , P.R. e , B.R. e , C.R. e R f , and SiR e R f selected from the group consisting of; Y 1 ~Y 13 each is independently selected from the group consisting of C and N; Y' is BR e , B.R. e R f , N.R. e , P.R. e , P(O)R e , O, S, Se, C=O, C=S, C=Se, C=NR e , C=CR e R f , S=O, SO2, CR e R f , SiR e R f , and GeR e R f selected from the group consisting of; R e and R f can be fused or linked to form a ring; Each R a , R b , R c , and R d independently represent one substitution up to the maximum permitted number of substitutions, or no substitution; R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e , and R feach is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; R a1 , R b1 , R c1 , R d1 , R a , R b , R c , and R d Any two substituents of can be fused or linked to form a ring or to form a multidentate ligand.

[0218] In some embodiments, L B would result in the following structure in Listing 11: [ka] [ka] [ka] [ka] [ka] [ka] selected from the group consisting of; L C Listing 11 and [ka] selected from the group consisting of; During the ceremony, R a ', R b ', R c ', R d ' and R e each ' independently represents zero substitutions, one substitution, or up to the maximum allowed number of substitutions on its associated ring; R a ', R b ', R c ', Rd ' and R e ' are each independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; R a ', R b ', R c ', R d ', and R e The two substituents of may be fused or linked to form a ring or to form a multidentate ligand.

[0219] In some embodiments, the compound has the formula Ir(L A )(L Bk ) 2, formula Ir(L A )2(L Bk ), formula Ir(L A )2(L C ), or Ir(L A )(L Bk )(L C ), wherein L A , L A 1-(R1)(R1)(R1)(Y1)~L A 12-(R411)(R411)(R411)(Y50), L A 13-(R1)(R1)(R1)(Y1)(Y1)~L A 26-(R411)(R411)(R411)(Y50)(Y50), L A’ 1-(R1)(R2)(R1)(Y1)~L A’ 38-(R411)(R411)(R411)(Y50), and L A’ 39-(R1)(R2)(R1)(Y1)(Y1)~L A’ 80-(R411)(R411)(R411)(Y50)(Y50); In the formula, k is an integer from 1 to 530, and each L Bk is the structure defined in Listing 12: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] having; Each L Cj-I is the formula [ka] having a structure based on Each L Cj-II is the formula [ka] It has a structure based on L Cj-I and L Cj-II Each L Cj About R 201 and R 202 can be used independently in the following list: [ka] [ka] [ka] [ka] [ka] [ka] [ka] is defined as R D1 ~R D246 would result in the following structure in Listing 14: [ka] [ka] [ka] has.

[0220] In some embodiments, the compound has its L Bk Below: B1 , L B30 , L B31 , L B109 , L B110 , L B112 , L B113 , L B114 , L B125 , L B127 , L B138 , L B140 , L B149 , L B150 , L B170 , L B171 , L B172 , L B174 , L B208 , L B241 , L B312 , L B315 , L B356 , L B367 , L B371 , L B382 , L B439 , L B440 , L B455 , L B456 , L B457 , L B458 , L B461 , L B462 , L B463 , L B469 , and LB476 The compound is selected from the group consisting of compounds which correspond to one of the following:

[0221] In some embodiments, the compound has its L Bk Below: B1 , L B30 , L B31 , L B125 , L B138 , L B171 , L B172 , L B356 , L B367 , L B371 , L B382 , L B455 , and L B456 The compound is selected from the group consisting of compounds which correspond to one of the following:

[0222] In some embodiments, the compound has its corresponding R 201 and R 202 has the following structure: D1 , R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D18 , R D20 , R D22 , R D37 , R D40 , R D41 , R D42 , R D43 , R D48 , R D49 , R D50 , R D54 , R D55 , R D58 , R D59 , R D78 , R D79 , R D81 , R D87 , R D88 , R D89 , R D93 , R D116 , R D117 , R D118 , R D119 , R D120 , R D133 , R D134 , R D135 , R D136, R D143 , R D144 , R D145 , R D146 , R D147 , R D149 , R D151 , R D154 , R D155 , R D161 , R D175 , R D190 , R D193 , R D200 , R D201 , R D206 , R D210 , R D214 , R D215 , R D216 , R D218 , R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 , and R D246 L defined as one of Cj-I Or L Cj-II The compound is selected from the group consisting of only compounds having ligands.

[0223] In some embodiments, the compound has its corresponding R 201 and R 202 However, the following structure: D1 , R D3 , R D4 , R D5 , R D9 , R D10 , R D17 , R D22 , R D43 , R D50 , R D78 , R D116 , R D118 , R D133 , R D134 , R D135 , R D136 , R D143 , R D144 , R D145 , R D146 , R D149 , R D151 , R D154 , R D155 , R D190 , RD193 , R D200 , R D201 , R D206 , R D210 , R D214 , R D215 , R D216 , R D218 , R D219 , R D220 , R D227 , R D237 , R D241 , R D242 , R D245 , and R D246 L defined as one selected from Cj-I Or L Cj-II The compound is selected from the group consisting of only compounds having ligands.

[0224] In some embodiments, the compound is L Cj-I The ligands are shown in the following List 15 structures: [ka] [ka] In some embodiments, L A is selected from the group consisting of structures of List 4, List 5, List 6 and List 7. In some embodiments, L B is selected from the group consisting of structures of List 10, List 11 and List 12. In some embodiments, L A is L as defined herein. A 1-(R1)(R1)(R1)(Y1)~L A 21-(R411)(R411)(R411)(Y50) Ai (R J )(R K )(R L )(Y M ) and L A 22-(R1)(R1)(R1)(Y1)(Y1)~L A 64-(R411)(R411)(R411)(Y50)(Y50) Ai’ (R J)(R K )(R L )(Y M )(Y N ) selected from the group consisting of structures in List 6 of L B is L as defined herein. B1 ~L B530 L consisting of Bk In some embodiments, L is selected from the group consisting of list 12. A is L as defined herein. A’ 1-(R1)(R2)(R1)(Y1)~L A’ 38-(R411)(R411)(R411)(Y50) A’i’’ (R J )(R K’ )(R L )(Y M ) and L A’ 39-(R1)(R2)(R1)(Y1)(Y1)~L A’ 78-(R411)(R411)(R411)(Y50)(Y50) A’i’’’ (R J )(R K’ )(R L )(Y M )(Y N ) selected from the group consisting of structures in List 7 of L B is L as defined herein. B1 ~L B530 L consisting of Bk The compound is selected from the group consisting of list 12 of:

[0225] In some embodiments, the compound is Ir(L A )2(L B ), Ir(L A )(L B )2, or Ir(L A )(L B )(L C ).

[0226] In some embodiments, the compound is Ir(L Ai (R J )(R K )(R L )(Y M ))2(L B), Ir(L Ai’ (R J )(R K )(R L )(Y M )(Y N ))2(L B ), Ir(L Ai (R J )(R K )(R L )(Y M ))(L B )2, Ir(L Ai’ (R J )(R K )(R L )(Y M )(Y N ))(L B )2, Ir(L Ai’’ (R J )(R K’ )(R L )(Y M ))2(L B ), Ir(L Ai’’’ (R J )(R K’ )(R L )(Y M )(Y N ))2(L B ), Ir(L Ai’’ (R J )(R K’ )(R L )(Y M ))(L B )2, and Ir(L Ai’’’ (R J )(R K’ )(R L )(Y M )(Y N ))(L B In some embodiments, the compound can be Ir(L A 1-(R1)(R1)(R1)(Y1))2(L B1 )~Ir(L A 21-(R411)(R411)(R411)(Y50))2(L B530 ) compound Ir(L Ai (R J )(R K )(R L )(Y M ))2(LBk ), Ir(L A 22-(R1)(R1)(R1)(Y1)(Y1))2(L B1 )~Ir(L A 64-(R411)(R411)(R411)(Y50)(Y50))2(L B530 ) compound Ir(L Ai’ (R J )(R K )(R L )(Y M )(Y N ))2(L Bk ), Ir(L A’ 1-(R1)(R2)(R1)(Y1))2(L B1 )~Ir(L A’ 38-(R411)(R411)(R411)(Y50))2(L B530 ) compound Ir(L A’i’’ (R J )(R K’ )(R L )(Y M ))2(L Bk ), Ir(L A’ 39-(R1)(R2)(R1)(Y1)(Y1))2(L B1 )~Ir(L A’ 78-(R411)(R411)(R411)(Y50)(Y50))2(L B530 ) compound Ir(L A’i’’’ (R J )(R K’ )(R L )(Y M )(Y N ))2(L Bk ), Ir(L A 1-(R1)(R1)(R1)(Y1))(L B1 )2~Ir(L A 21-(R411)(R411)(R411)(Y50))(L B530 )2 compound Ir(L Ai (R J )(R K )(R L )(Y M ))(L Bk )2, Ir(L A 22-(R1)(R1)(R1)(Y1)(Y1))(LB1 )2~Ir(L A 64-(R411)(R411)(R411)(Y50)(Y50))(L B530 )2 compound Ir(L Ai’ (R J )(R K )(R L )(Y M )(Y N ))(L Bk )2, Ir(L A’ 1-(R1)(R2)(R1)(Y1))(L B1 )2~Ir(L A’ 38-(R411)(R411)(R411)(Y50))(L B530 )2 compound Ir(L A’i’’’ (R J )(R K’ )(R L )(Y M ))(L Bk )2, and Ir(L A’ 39-(R1)(R2)(R1)(Y1)(Y1))(L B1 )2~Ir(L A’ 78-(R411)(R411)(R411)(Y50)(Y50))(L B530 )2 compound Ir(L A’i’’’ (R J )(R K’ )(R L )(Y M )(Y N ))(L Bk ) 2.

[0227] In some embodiments, the compound is Ir(L A 1-(R1)(R1)(R1)(Y1))(L B1 )(L C1-I )~Ir(L A 21-(R411)(R411)(R411)(Y50))(L B530 )(L C1416-I ) compound Ir(L Ai (R J )(R K )(R L )(Y M ))(L Bk )(LCJ-I ), Ir(L A 22-(R1)(R1)(R1)(Y1)(Y1))(L B1 )(L C1-I )~Ir(L A 64-(R411)(R411)(R411)(Y50)(Y50))(L B530 )(L C1416-I ) compound Ir(L Ai’ (R J )(R K )(R L )(Y M )(Y N ))(L Bk )(L CJ-I ), Ir(L A 1-(R1)(R1)(R1)(Y1))(L B1 )(L C1-II )~Ir(L A 21-(R411)(R411)(R411)(Y50))(L B530 )(L C1416-II ) compound Ir(L Ai (R J )(R K )(R L )(Y M ))(L Bk )(L CJ-II ), and Ir(L A 22-(R1)(R1)(R1)(Y1)(Y1))(L B1 )(L C1-II )~Ir(L A 64-(R411)(R411)(R411)(Y50)(Y50))(L B530 )(L C1416-II ) compound Ir(L Ai (R J )(R K )(R L )(Y M )(Y N ))(L Bk )(L CJ-II ).

[0228] In some embodiments, the compound is Ir(L A’ 1-(R1)(R2)(R1)(Y1))(L B1 )(L C1-I)~Ir(L A 38-(R411)(R411)(R411)(Y50))(L B530 )(L C1416-I ) compound Ir(L A’i’’ (R J )(R K’ )(R L )(Y M )(Y N ) g )(L Bk )(L CJ-I ), Ir(L A’ 39-(R1)(R2)(R1)(Y1)(Y1))(L B1 )(L C1-I )~Ir(L A’ 78-(R411)(R411)(R411)(Y50)(Y50))(L B530 )(L C1416-I ) compound Ir(L A’i’’’ (R J )(R K’ )(R L )(Y M )(Y N ))(L Bk )(L CJ-I ), Ir(L A’ 1-(R1)(R2)(R1)(Y1))(L B1 )(L C1-II )~Ir(L A’ 38-(R411)(R411)(R411)(Y50))(L B530 )(L C1416-II ) compound Ir(L A’i’’ (R J )(R K’ )(R L )(Y M ))(L Bk )(L CJ-II ), and Ir(L A’ 39-(R1)(R2)(R1)(Y1)(Y1))(L B1 )(L C1-II )~Ir(L A’ 78-(R411)(R411)(R411)(Y50)(Y50))(L B530 )(L C1416-II ) compound Ir(L A’i’’’ (R J )(RK’ )(R L )(Y M )(Y N ))(L Bk )(L CJ-II ).

[0229] In some embodiments, the compound has the structure of List 16 below: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] is selected from the group consisting of:

[0230] In another aspect, the present disclosure provides the following List W1: [ka] [ka] (In the formula, Y B and Y C are independently defined as defined herein.

[0231] In some such embodiments, each Y B and Y C is independently selected from the group consisting of O, S, Se, and C(CH). In some embodiments, each Y B and Y C is independently selected from the group consisting of O and C(CH). In some embodiments, each Y B and Y C is O. In some embodiments, Y B Or Y C is O and Y B Or Y C The other is C(CH). In some embodiments, Y B and Y C Both exist.

[0232] In yet another aspect, the present disclosure provides the following List W2: [ka] (In the formula, Y B and Y C are independently defined as defined herein.

[0233] In some such embodiments, each Y B and Y C is independently selected from the group consisting of O, S, Se, and C(CH). In some embodiments, each Y B and Y C is independently selected from the group consisting of O and C(CH). In some embodiments, each Y B and Y C is O. In some embodiments, Y B Or Y C is O and Y B Or Y C The other is C(CH). In some embodiments, Y B and Y C Both exist.

[0234] It should be understood that if a structure is selected from List W1 or List W2, further modifications may be required to satisfy one or more limitations of claim 1 or its dependent claims, and those modifications should be considered within the scope of this disclosure.

[0235] In some embodiments, the first ligand L of formula I described herein A The compound having the formula (I) may 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, percent deuterated has its usual meaning and includes the percent of all available hydrogen atoms in the compound (e.g., positions that are hydrogen or deuterium) that are occupied by deuterium atoms. In some embodiments, the carbon atoms that make up the ring coordinated to the metal M are fully or partially deuterated. In some embodiments, the carbon atoms included in the polycyclic ring system coordinated to the metal M are fully or partially deuterated. In some embodiments, the substituents attached to the monocyclic or fused polycyclic ring system coordinated to the metal M are fully or partially deuterated.

[0236] In some embodiments, the compounds of formula I have a full width at half maximum (FWHM) emission at room temperature of 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, or 5 nm or less. A narrower FWHM means better color purity for OLED display applications.

[0237] As defined above, M(L A ) p (L B ) q (L C ) r In some embodiments of the heteroleptic compound having the formula A is the first substituent R I and the first substituent R I is the ligand L AAmong all atoms in the metal M, the first atom aI is the furthest from the metal M. In addition, the ligand L B is, if present, a second substituent R II and a second substituent R II is the ligand L B Among all atoms in the ligand L, the first atom a-II is the furthest from the metal M. C If present, the third substituent R III and a third substituent R III is the ligand L C Among all the atoms in the structure, the first atom a-III is the one furthest from the metal M.

[0238] In such heteroleptic compounds, the vector V D1 , V D2 , and V D3 can be defined as follows: V D1 represents the direction from the metal M to the first atom aI, and the vector V D1 is the first substituent R I A value D representing the linear distance between the metal M and the first atom aI in 1 V D2 represents the direction from the metal M to the first atom a-II, and the vector V D2 is the second substituent R II The value D represents the linear distance between the metal M and the first atom a-II in 2 V D3 represents the direction from the metal M to the first atom a-III, and the vector V D3 is a third substituent R III The value D represents the linear distance between the metal M and the first atom a-III in 3 has.

[0239] In such heteroleptic compounds, a sphere with radius r is defined with the metal M at its center, and the radius r is the radius of the sphere when the substituent R I , R II and R III is the smallest radius that allows enclosing all atoms in the compound that are not part of D 1 , D 2 , and D 3At least one of D is at least 1.5 Å greater than the radius r. 1 , D 2 , and D 3 At least one of D is at least 2.9 Å, 3.0 Å, 4.3 Å, 4.4 Å, 5.2 Å, 5.9 Å, 7.3 Å, 8.8 Å, 10.3 Å, 13.1 Å, 17.6 Å, or 19.1 Å greater than the radius r. 1 , D 2 , and D 3 At least two of are at least 1.5 Å, 2.9 Å, 3.0 Å, 4.3 Å, 4.4 Å, 5.2 Å, 5.9 Å, 7.3 Å, 8.8 Å, 10.3 Å, 13.1 Å, 17.6 Å, or 19.1 Å greater than the radius r.

[0240] In some embodiments of such heteroleptic compounds, the compound has a transition dipole moment axis and a vector V D1 , V D2 , and V D3 An angle is defined between the transition dipole moment axis and the vector V D1 , V D2 , and V D3 At least one of the angles between the transition dipole moment axis and the vector V is less than 40°. D1 , V D2 , and V D3 At least one of the angles between the transition dipole moment axis and the vector V D1 , V D2 , and V D3 At least two of the angles between the transition dipole moment axis and the vector V D1 , V D2 , and V D3 At least two of the angles between are less than 15° or 10°.

[0241] In some embodiments, the transition dipole moment axis and the vector V D1 , V D2 , and V D3All three angles between the transition dipole moment axis and the vector V are less than 20°. D1 , V D2 , and V D3 All three angles between are less than 15° or 10°.

[0242] In some embodiments of such heteroleptic compounds, the compounds have a vertical dipole ratio (VDR) of 0.33 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.30, 0.25, 0.20, or 0.15 or less.

[0243] Those skilled in the art will easily understand the meaning of the terms transition dipole moment axis of a compound and vertical dipole ratio of a compound. Nevertheless, the meaning of these terms can be found in U.S. Pat. No. 10,672,997, the disclosure of which is incorporated herein by reference in its entirety. In U.S. Pat. No. 10,672,997, the horizontal dipole ratio (HDR) of a compound is discussed, not the VDR. However, those skilled in the art will easily understand that VDR=1-HDR.

[0244] In some embodiments, the compound may be an emissive dopant. In some embodiments, the compound may generate luminescence via phosphorescence, fluorescence, thermally activated delayed fluorescence, triplet-triplet annihilation, or a combination of these processes. In some embodiments, the emissive dopant may be a racemic mixture or may be enriched in one enantiomer. In some embodiments, the compound may have different stereoisomers, such as fac and mer. The compound relates to both individual isomers and mixtures of various isomers in any mixture ratio. In some embodiments, the compound may be homoleptic (each ligand is the same). In some embodiments, the compound may be heteroleptic (at least one ligand is different from the others). When there are multiple ligands coordinated to the metal, in some embodiments, the ligands may all be the same. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, all ligands may be different from all other ligands. This is also true in embodiments where a ligand coordinated to a metal can be linked to other ligands coordinated to the metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligand. Thus, when the coordinating ligands are linked together, in some embodiments, all of the ligands can be the same, and at least one of the linked ligands can be different from the others in some other embodiments.

[0245] In yet another aspect of the present disclosure, a formulation is described that includes the novel compound disclosed herein.The formulation may include one or more components selected from the group consisting of the solvent, emitter, host, hole injection material, hole transport material, electron blocking material, hole blocking material, and electron transport material disclosed herein.

[0246] The present disclosure encompasses any chemical structure that includes the novel compounds of the present disclosure, or monovalent or polyvalent variants thereof. In other words, the compounds of the present invention, or monovalent or polyvalent variants thereof, can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of monomers, polymers, macromolecules, and supramolecules (also known as macromolecules). As used herein, a "monovalent variant of a compound" refers to a moiety that is identical to the compound, except that one hydrogen has been removed and replaced with a bond to the remainder of the chemical structure. As used herein, a "polyvalent variant of a compound" refers to a moiety that is identical to the compound, except that two or more hydrogens have been removed and replaced with bonds to the remainder of the chemical structure. In the example of a supramolecule, the compounds of the present invention can also be incorporated into a supramolecular complex without a covalent bond. As used in this context, the statement that structure A includes a B moiety means that structure A includes a structure of the B moiety that does not include an H atom or D atom that can be bonded to the B moiety. This is because at least one H or D on a given moiety must be replaced to become a substituent so that the B moiety can become part of structure A, and one or more H or D on a given B moiety can be further substituted once it becomes part of structure A.

[0247] C. OLEDs and Devices of the Present Disclosure In another aspect, the present disclosure also provides an OLED device comprising a first organic layer comprising a compound disclosed in the above Compounds section of this disclosure.

[0248] In some embodiments, an OLED comprises an anode; a cathode; and an organic layer disposed between the anode and the cathode, the organic layer having a formula Ir(L A ) x (L B ) y (L C ) z This includes compounds of the formula:

[0249] In some embodiments, the organic layer is selected from the group consisting of a HIL, a HTL, an EBL, an EML, a HBL, an ETL, and an EIL. In some embodiments, the organic layer can be an emissive layer, and the compounds described herein can be an emissive or non-emissive dopant.

[0250] In some embodiments, the organic layer can further include a host, the host being 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, azaborinine, oxaborinine, dihydroacridine, xanthene, dihydrobenzoazasiline, dibenzoxasiline, phenoxazine, phenoxathiin, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boryl, silyl, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ 2 -contains at least one chemical group selected from the group consisting of benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

[0251] In some embodiments, the host has the following host group 1 structure: [ka] [ka] [ka] [ka] [ka] (In the formula, Each of J1 to J6 is independently C or N; L' is a direct bond or an organic linker; Each Y AA , Y BB , Y CC and Y DD is independently selected from the group consisting of no bond, a direct bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, and BRR'; R A’ , R B’ , R C’ , R D’ , R E’ , R F’ , and R G’ each independently represents from one substitution to maximal substitution, or no substitution; Each R, R', R A’ , R B’ , R C’ , R D’ , R E’ , R F’ , and R G’ are independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents may be joined or fused to form a ring; and where possible, each unsubstituted aromatic carbon atom may be optionally replaced with one or more N to form an aza-substituted ring.

[0252] In some embodiments, L' is an organic linker selected from the group consisting of 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', GeRR', alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof.

[0253] In some embodiments, at least one of J1-J3 is N. In some embodiments, at least two of J1-J3 are N. In some embodiments, all three of J1-J3 are N. In some embodiments, each Y CC and Y DD is independently O, S, or SiRR', or more preferably O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is replaced with N to form an azacycle.

[0254] In some embodiments, the host is selected from the group consisting of EG1-MG1-EG1 through EG53-MG27-EG53, having the formula EGa-MGb-EGc, or, when MGb is absent, EG1-EG1 through EG53-EG53, having the formula EGa-EGc, where a is an integer from 1 to 53, b is an integer from 1 to 27, and c is an integer from 1 to 53. The structures of EG1 through EG53 are shown below. [ka] The structures of MG1 to MG27 are shown below: [ka] In the MGb structure shown above, the two binding positions in the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are labeled with numbers for identification purposes.

[0255] In some embodiments, the host may be any of its aza-substituted variants, fully or partially deuterated variants, and combinations thereof. In some embodiments, the host has the formula EGa-MGb-Egc and is selected from the group consisting of h1 through h112 defined in the Host Group 2 list below, where MGb, EGa, and EGc are each defined as follows: [ka] In the above table, the EGa and EGc structures that are bound to one of the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are indicated with a numeric prefix that identifies their binding position in the MGb structure.

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

[0257] In some embodiments, the light-emitting layer may include two hosts, a first host and a second host. In some embodiments, the first host is a hole-transporting host and the second host is an electron-transporting host. In some embodiments, the first host is a hole-transporting host and the second host is a bipolar host. In some embodiments, the first host is an electron-transporting host and the second host is a bipolar host. In some embodiments, the first host and the second host may form an exciplex. In some embodiments, the light-emitting layer may include a third host. In some embodiments, the third host is selected from the group consisting of insulating hosts (wide band gap hosts), hole-transporting hosts and electron-transporting hosts. In some embodiments, the third host forms an exciplex with one of the first host and the second host or with both the first host and the second host. In some embodiments, the light-emitting layer may include a fourth host. In some embodiments, the fourth host is selected from the group consisting of insulating hosts (wide band gap hosts), hole transporting hosts, and electron transporting hosts. In some embodiments, the fourth host forms an exciplex with one of the first host, the second host, and the third host, with two of the first host, the second host, and the third host, or with each of the first host, the second host, and the third host. In some embodiments, the electron transporting host has a LUMO less than -2.4 eV, less than -2.5 eV, less than -2.6 eV, or less than -2.7 eV. In some embodiments, the hole transporting host has a HOMO greater than -5.6 eV, greater than -5.5 eV, greater than -5.4 eV, or greater than -5.35 eV. The HOMO and LUMO values ​​can be determined using solution electrochemistry. Solution cyclic voltammetry and differential pulse voltammetry can be performed using a CH Instruments model 6201B potentiostat using anhydrous dimethylformamide (DMF) solvent and tetrabutylammonium hexafluorophosphate as the supporting electrolyte. Glassy carbon, platinum wire, and silver wire were used as the working, counter, and reference electrodes, respectively.The electrochemical potential was determined by measuring the peak potential difference from differential pulse voltammetry for the internal ferrocene-ferrocenium redox couple (Fc / Fc. + By referencing the cation and anion redox potentials to ferrocene (4.8 eV vs. vacuum), the corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies can be determined according to the following references: (a) Fink, R.; Heischkel, Y.; Thelakkat, M.; Schmidt, H.-W. Chem. Mater. 1998, 10, 3620-3625; (b) Pommerehne, J.; Vestweber, H.; Guss, W.; Mahrt, RF; Bassler, H.; Porsch, M.; Daub, J. Adv. Mater. 1995, 7, 551).

[0258] In some embodiments, the compounds described herein may be sensitizers or components of sensitizers, and the device may further include an acceptor that receives energy from the sensitizer. In some embodiments, the acceptor is an emitter in the device. In some embodiments, the acceptor may be a fluorescent material. In some embodiments, the compounds described herein may be used as phosphorescent sensitizers in OLEDs where one or more layers in the OLED include an acceptor in the form of one or more non-delayed fluorescent and / or delayed fluorescent materials. In some embodiments, the compounds described herein may be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor, which will either emit energy or further transfer energy to the final emitter. The concentration of the acceptor may range from 0.001% to 99.9%. The acceptor may be present either in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a thermally activated delayed fluorescent (TADF) material. In some embodiments, the acceptor is a non-delayed fluorescent material. In some embodiments, the emission can come from any or all of the sensitizer, the acceptor, and the final emitter. In some embodiments, the acceptor has a room temperature emission with a full width at half maximum (FWHM) of 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, or 5 nm or less. A narrower FWHM means better color purity for OLED display applications.

[0259] As used herein, phosphorescence generally refers to the emission of photons with a change in electron spin quantum number. That is, the initial and final states of emission have different electron spin quantum numbers, such as T1 to S0 state. Most of the Ir and Pt complexes currently used in OLEDs are phosphorescent emitters. In some embodiments, when exciplex formation involves triplet emitters, such exciplexes can also emit phosphorescence. On the other hand, fluorescent emitters generally refer to the emission of photons without a change in electron spin quantum number, such as S1 to S0 state or D1 to D0 state. Fluorescent emitters can be delayed fluorescent emitters or non-delayed fluorescent emitters. Depending on the spin state, fluorescent emitters can be singlet or doublet emitters, or other multiplet emitters. It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistical limit due to delayed fluorescence. There are two types of delayed fluorescence, namely P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence arises from triplet-triplet annihilation (TTA). On the other hand, E-type delayed fluorescence does not depend on the collision of two triplets, but rather on the thermal population between the triplet state and the singlet excited state. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as TADF. E-type delayed fluorescence properties can be found in exciplex systems or single compounds. Without being bound by theory, TADF emission is characterized by a small singlet-triplet energy gap (ΔE S-T) is believed to be required. There are two main types of TADF emitters, one is called donor-acceptor type TADF and the other is called multiple resonance (MR) TADF. In many cases, single compound donor-acceptor TADF compounds are constructed by connecting an electron donor moiety, such as an amino derivative or carbazole derivative, with an electron acceptor moiety, such as an N-containing six-membered aromatic ring or a cyano-substituted aromatic ring. A donor-acceptor exciplex can be formed between a hole transport compound and an electron transport compound. Examples of MR-TADF materials include highly conjugated fused ring systems. In some embodiments, MR-TADF materials include boron, carbon, and nitrogen atoms. Such materials may also include other atoms, such as oxygen. In some embodiments, the reverse intersystem crossing time from T1 to S1 of delayed fluorescence emission at 293 K is 10 microseconds or less. In some embodiments, such a time can be greater than 10 microseconds and less than 100 microseconds.

[0260] In some embodiments, the OLED may include an additional compound selected from the group consisting of a non-delayed fluorescent material, a delayed fluorescent material, a phosphorescent material, and combinations thereof.

[0261] In some embodiments, the compounds of the invention described herein are phosphorescent materials.

[0262] In some embodiments, the phosphorescent material is an emitter that emits light in the OLED. In some embodiments, the phosphorescent material does not emit light in the OLED. In some embodiments, the energy of the phosphorescent material transfers its excited state to another material in the OLED. In some embodiments, the phosphorescent material participates in charge transport in the OLED. In some embodiments, the phosphorescent material is a sensitizer or a component of a sensitizer, and the OLED further includes an acceptor. In some embodiments, the phosphorescent material forms an exciplex with another material in the OLED, e.g., a host material, an emitter material.

[0263] In some embodiments, the non-delayed fluorescent material or delayed fluorescent material is an emitter that emits light in the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material does not emit light in the OLED. In some embodiments, the energy of the non-delayed fluorescent material or delayed fluorescent material transfers its excited state to another material in the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material participates in charge transport in the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material is an acceptor, and the OLED further comprises a sensitizer.

[0264] In some embodiments of the OLED, the delayed fluorescent material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescent material is a metal complex. In some embodiments, the delayed fluorescent material is a non-metal complex. In some embodiments, the delayed fluorescent material is a Pt, Pd, Zn, Cu, Ag, or Au complex (some of which are also called metal-assisted (MA) TADF). In some embodiments, the metal-assisted delayed fluorescent material comprises a metal-carbene bond. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material is an aryl-amine, aryloxy, arylthio, 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, 5λ 2 ,9λ 2 -diaza-13b-boranaphtho[2,3,4-de]anthracene, 5-oxa-9λ 2-aza-13b-boranaphtho[3,2,1-de]anthracene, azaborinine, oxaborinine, dihydroacridine, xanthene, dihydrobenzoazasiline, dibenzoxasiline, phenoxazine, phenoxathiin, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boryl, amino, silyl, aza-variants thereof, and combinations thereof. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material comprises a tri(aryl / heteroaryl)borane in which one or more pairs of aryl / heteroaryl-derived substituents are bonded to form a ring. In some embodiments, the fluorescent material includes at least one chemical group selected from the group consisting of naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene.

[0265] In yet another aspect, the OLED of the present disclosure may also include a light-emitting region comprising a compound or a combination of compounds disclosed in the above Compounds section of this disclosure. In some embodiments, the light-emitting region comprises a compound of formula Ir(L A ) x (L B ) y (L C ) zor a formulation containing the compound. In some embodiments, the light-emitting region is comprised of one or more organic layers, and at least one of the one or more organic layers has a minimum thickness selected from the group consisting of 350 Å, 400 Å, 450 Å, 500 Å, 550 Å, 600 Å, 650 Å, and 700 Å. In some embodiments, at least one of the one or more organic layers is formed from a light-emitting system having a figure of merit (FOM) value equal to or greater than a number selected from the group consisting of 2.50, 2.55, 2.60, 2.65, 2.70, 2.75, 2.80, 2.85, 2.90, 2.95, 3.00, 5.00, 10.0, 15.0, and 20.0. A definition of FOM is available in U.S. Patent Application Publication No. 2023 / 0292605, the entire contents of which are incorporated herein by reference. In some embodiments, at least one of the one or more organic layers comprises a compound or a combination of compounds disclosed in Sections A and D of this disclosure.

[0266] In some embodiments, an OLED or light-emitting region comprising the compounds of the present invention disclosed herein can be incorporated into a full-color pixel array of a device. The full-color pixel array of such a device comprises at least one pixel, and at least one pixel comprises a first subpixel and a second subpixel. The first subpixel comprises a first OLED comprising a first light-emitting region. The second subpixel comprises a second OLED comprising a second light-emitting region. In some embodiments, the first and / or second OLED, the first and / or second light-emitting region can be the same or different, and each can independently have various device characteristics and various embodiments of the compounds of the present invention contained therein, as well as various combinations and subcombinations of various device characteristics and various embodiments of the compounds of the present invention contained therein, as disclosed herein.

[0267] In some embodiments, the first light-emitting region has a peak wavelength, λ max1 and the second light-emitting region is configured to emit light having a peak wavelength λ max2In some embodiments, the light source is configured to emit light having a peak wavelength λ max1 and λ max2 The difference between the peak wavelengths λ and λ 2 is at least 4 nm, but within the same color range. For example, the light blue and dark blue light mentioned above. In some embodiments, the first light-emitting region has a peak wavelength λ 2 in one of the regions of the visible spectrum of 400 to 500 nm, 500 to 600 nm, or 600 to 700 nm. max1 and the second light-emitting region is configured to emit light having a peak wavelength λ in one of the remaining regions of the visible spectrum of 400-500 nm, 500-600 nm, or 600-700 nm. max2 In some embodiments, the first light-emitting region includes a first number of light-emitting layers, if more than one, stacked on top of one another, and the second light-emitting region includes a second number of light-emitting layers, if more than one, stacked on top of one another, the first number being different from the second number. In some embodiments, both the first light-emitting region and the second light-emitting region include phosphorescent materials, which may be the same or different. In some embodiments, the first light-emitting region includes phosphorescent materials, and the second light-emitting region includes fluorescent materials. In some embodiments, both the first light-emitting region and the second light-emitting region include fluorescent materials, which may be the same or different.

[0268] In some embodiments, at least one pixel of an OLED or light-emitting region includes a total of N sub-pixels, the N sub-pixels including the first sub-pixel and the second sub-pixel, each of the N sub-pixels includes a light-emitting region, and the total number of light-emitting regions in the at least one pixel is N-1 or less. In some embodiments, the second light-emitting region is identical to the first light-emitting region, and each sub-pixel of the at least one pixel includes one light-emitting region that is identical to the first light-emitting region. In some embodiments, the full color pixel array may have a plurality of pixels including a first pixel region and a second pixel region, and at least one display characteristic in the first pixel region is different from a corresponding display characteristic in the second pixel region, and the at least one display characteristic is selected from the group consisting of resolution, cavity mode, color, outcoupling, and color filter.

[0269] In some embodiments, the OLED is a stacked OLED including one or more charge generating layers (CGLs). In some embodiments, the OLED includes a first electrode, a first light-emitting region disposed on the first electrode, a first CGL disposed on the first light-emitting region, a second light-emitting region disposed on the first CGL, and a second electrode disposed on the second light-emitting region. In some embodiments, the first and / or second light-emitting regions can have various device characteristics as described above for the pixelated device. In some embodiments, the stacked OLED is configured to emit white light. In some embodiments, one or more light-emitting regions in a pixelated OLED or stacked OLED include sensitizers and acceptors having the various sensitizing device characteristics and various embodiments of the compounds of the present invention disclosed herein. For example, the first light-emitting region is included in a sensitizing device and the second light-emitting region is not included in a sensitizing device, and in some examples, both the first and second light-emitting regions are included in a sensitizing device.

[0270] In some embodiments, the OLED can emit at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99% or 100% of light from the plasmonic mode. In some embodiments, at least one of the anode, the cathode, or a new layer disposed on the organic light-emitting layer functions as an enhancement layer. The enhancement layer includes a plasmonic material that non-radiatively couples to the emitter material and exhibits a surface plasmon resonance that transfers excited state energy from the emitter material to a non-radiative mode of surface plasmon polariton. In some embodiments, the enhancement layer is disposed within a threshold distance from the organic light-emitting layer, and the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer. At the threshold distance, the total non-radiative decay rate constant is equal to the total radiative decay rate constant. Another threshold distance is the distance at which the total radioactive decay rate constant divided by the sum of the total non-radioactive decay rate constant and the total radioactive decay rate constant equals the photoluminescence yield of the luminescent material in the absence of the enhancement layer.

[0271] In some embodiments, the OLED further includes an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the enhancement layer opposite the organic light emitting layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, the energy is scattered as photons into free space. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device, such as, but not limited to, an organic waveguide mode, a substrate mode, or another waveguide mode. In some embodiments, one or more intervening layers can be disposed between the enhancement layer and the outcoupling layer. Examples of intervening layers can be dielectric materials, including organic, inorganic, perovskite, oxides, and can include stacks and / or mixtures of these materials.

[0272] The enhancement layer alters the effective properties of the medium in which the emitter material resides, resulting in any or all of the following: reduced emission rate, altered emission line shape, change in emission intensity with angle, change in stability of the emitter material, change in efficiency of the OLED, and reduced efficiency roll-off of the OLED device. Placing an enhancement layer on the cathode side, anode side, or both, or placing the enhancement layer itself as a CGL, results in an OLED device that utilizes any of the above effects. In addition to the specific functional layers shown in the various OLED examples described and illustrated herein, OLEDs according to the present disclosure can include any of the other functional layers frequently found in OLEDs.

[0273] In some embodiments, the enhancement layer may be comprised of a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. In some embodiments, the plasmonic material includes at least one metal. In such embodiments, the metal may include at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, or Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has periodically, quasi-periodically, or randomly arranged wavelength-sized features, or periodically, quasi-periodically, or randomly arranged sub-wavelength-sized features.

[0274] In some embodiments, the outcoupling layer has periodically, quasi-periodically, or randomly arranged wavelength-sized features or periodically, quasi-periodically, or randomly arranged sub-wavelength-sized features. In some embodiments, the outcoupling layer may be comprised of nanoparticles. In some embodiments, the outcoupling layer is comprised of nanoparticles arranged on a material. In these embodiments, the outcoupling layer may be tunable by at least one of changing the size of the nanoparticles, changing the shape of the nanoparticles, changing the material of the nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, adding an additional layer on the nanoparticles, changing the thickness of an enhancement layer, or changing the material of an enhancement layer. The nanoparticles of the device may be formed from at least one of a metal, a dielectric material, a semiconductor material, an alloy of a metal, a mixture of a dielectric material, a stack or layer of one or more materials, and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles, the metal being 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, and Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the outcoupling layer is formed by lithography.

[0275] In some embodiments of the plasmonic device, the emitters and / or host compounds used in the emissive layer have a vertical dipole ratio (VDR) of 0.33 or greater, and in some such embodiments, the emitters and / or host compounds have a VDR of 0.40, 0.50, 0.60, 0.70, or greater.

[0276] In yet another aspect, the present disclosure also provides a consumer product comprising an organic light emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound or a blend of compounds disclosed in the Compounds section of this disclosure above.

[0277] In some embodiments, a consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, the organic layer having a compound represented by formula Ir(L A ) x (L B ) y (L C ) z The compound may include:

[0278] In general, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an "exciton" is formed, which is a localized electron-hole pair having an excited energy state. Light is emitted via a photoemissive mechanism when the exciton relaxes. In some cases, the exciton may localize as an excimer or exciplex. Non-radiative mechanisms such as thermal relaxation may also occur, but are generally considered undesirable.

[0279] FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. The device 100 may include a substrate 110, an anode 115, a hole injection layer (HIL) 120, a hole transport layer (HTL) 125, an electron blocking layer (EBL) 130, an emissive layer (EML) 135, a hole blocking layer (HBL) 140, an electron transport layer (ETL) 145, an electron injection layer (EIL) 150, a protective layer 155, a cathode 160, and a barrier layer 170. The cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704, columns 6-10, which are incorporated by reference.

[0280] Further examples are available for each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use of blocking layers are described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated by reference in their entirety. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0281] FIG. 2 shows 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. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed above an anode, and device 200 has a cathode 215 disposed below anode 230, device 200 may be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides an example of how some layers may be omitted from the structure of device 100.

[0282] The simple layer structures illustrated in Figures 1 and 2 are provided as non-limiting examples, and it is understood that embodiments of the present disclosure may be used in conjunction with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. A functional OLED may be achieved by combining the various layers described in various ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. While many of the examples provided herein describe the various layers as including a single material, it is understood that combinations of materials, such as mixtures of hosts and dopants, or more generally mixtures, may be used. Layers may also have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include a single layer or may further include multiple layers of different organic materials, such as those described with respect to Figures 1 and 2.

[0283] Structures and materials not specifically described may be used, such as OLEDs (PLEDs) composed of polymeric materials such as those disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. As a further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example, as described in U.S. Pat. No. 5,707,745 to Forrest et al., which is incorporated by reference in its entirety. OLED structures may deviate from the simple layered structures illustrated in FIGS. 1 and 2. For example, the substrate may include angled reflective surfaces to improve outcoupling, such as the mesa structures described in U.S. Pat. No. 6,091,195 to Forrest et al. and / or the recessed structures described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0284] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include deposition by thermal evaporation, such as those described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entirety, inkjet, organic vapor phase deposition (OVPD), such as those described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and organic vapor jet printing (OVJP, also referred to as organic vapor jet deposition (OVJD)), such as those 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 a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation, sputtering, chemical vapor deposition, atomic layer deposition, and electron beam evaporation. Preferred patterning methods include deposition via mask, photolithography, and cold welding, such as those described in U.S. Patent Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety, as well as patterning associated with some of the deposition methods, such as inkjet and organic vapor jet printing (OVJP). Other methods may be used. The material to be deposited may be modified to be compatible with the particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents with 20 or more carbons may be used, with 3-20 carbons being a preferred range. Materials with asymmetric structures may have better solution processability than those with symmetric structures, as asymmetric materials may be less prone to recrystallization. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

[0285] Devices made according to embodiments of the present disclosure may further include an optional barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment, including moisture, vapors and / or gases, etc. The barrier layer may be deposited on, under or next to the substrate, the electrodes, or on any other portion of the device, including the edges. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by a variety of known chemical vapor deposition techniques and may include compositions having a single phase and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds or both. Preferred barrier layers include multiple alternating layers of polymeric and non-polymeric materials; organic and inorganic materials; or mixtures of polymeric and non-polymeric materials, by way of example only, as described in U.S. Pat. No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated by reference in their entireties.

[0286] Devices made according to embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into various electrical products or intermediate components. Examples of such electrical products or intermediate components include display screens, lighting devices, such as discrete light source devices or lighting panels, that can be utilized by end-user product manufacturers. Such electronic component modules can optionally include driving electronics and / or power sources. Devices made according to 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 are consumer products that include OLEDs that include compounds of the present disclosure in the organic layer of the OLED. Such consumer products include any type of product that includes one or more light sources and / or one or more visual displays of some kind. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for indoor or outdoor illumination and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays aligned together, theater or stadium screens, phototherapy devices, and signage. A variety of control mechanisms can be used to control devices made according to the present disclosure, including passive matrix and active matrix. Many of the devices are intended for use within a temperature range that is comfortable for humans, such as 18°C ​​to 30°C, and more preferably room temperature (20-25°C), but may also be used outside this temperature range, for example, at temperatures between -40°C and +80°C Celsius.

[0287] Further details regarding OLEDs and the above definitions can be found in US Pat. No. 7,279,704, which is incorporated by reference in its entirety.

[0288] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may use the materials and structures. More generally, organic devices such as organic transistors may use the materials and structures.

[0289] In some embodiments, the OLED has one or more properties selected from the group consisting of being flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes. In some embodiments, the OLED further comprises one or more quantum dots. Such quantum dots may be present in the emissive layer or other functional layers, such as a down-conversion layer.

[0290] In some embodiments, the OLED comprises an RGB pixel array or a white and color filter pixel array. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0291] D. Other Materials Used in OLEDs The materials described herein are useful for a particular layer in an OLED as various examples. They can also be used in combination with a wide variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in the EML by themselves or in conjunction with a wide variety of other emitters, hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or referenced below are non-limiting examples of materials that may be useful in combination with the compounds and devices disclosed herein, and one of ordinary skill in the art can readily consult the literature to identify other materials that may be useful in combination.

[0292] a) Conductive dopants: The charge transport layer is doped with a conductive dopant, which significantly changes the density of charge carriers and therefore its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductive dopant, and an n-type conductive dopant is used in the electron transport layer. In some embodiments, the conductive dopant comprises at least one chemical moiety selected from the group consisting of cyano, fluorinated aryl or heteroaryl, fluorinated alkyl or cycloalkyl, alkylene, heteroaryl, amide, benzodithiophene, and highly conjugated heteroaryl groups extended with acyclic double bonds.

[0293] b) HIL / HTL: The hole injection / transport material used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injection / transport material.Examples of materials include, but are not limited to, phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorocarbons; polymers with conductive dopants; conductive polymers such as PEDOT / PSS; self-assembly monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoOx; p-type semiconductor organic compounds such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile; metal complexes, and crosslinkable compounds.

[0294] Examples of aromatic amine derivatives used in HIL or HTL include those having the following general structure: [ka] These include, but are not limited to:

[0295] Ar 1 ~Ar 9each of which is a group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indole, and aromatic heterocyclic compounds such as xazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and aromatic hydrocarbon ring groups and aromatic heterocyclic groups, which may be the same or different groups and which 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 structure unit and an aliphatic ring group. 1 ~Ar 9 Each of may be unsubstituted or substituted with the general substituents described above, and any two substituents may be joined or fused to form a ring.

[0296] In some embodiments, each Ar 1 ~Ar 9 is, independently, [ka] (In the formula, k is an integer of 1 to 20; X 101 ~X108 is C or N; Z 101 is C, N, O, or S.

[0297] Examples of metal complexes used in the HIL or HTL include those of the general formula: [ka] (wherein Met is a metal that may have an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, and Y 101 and Y 102 are independently selected from C, N, O, P, and S; 101 are ancillary ligands; k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal; and k'+k'' is the maximum number of ligands that can be bound to the metal.

[0298] In some embodiments, (Y 101 -Y 102 ) is a 2-phenylpyridine or 2-phenylimidazole derivative. In some embodiments, (Y 101 -Y 102 In some embodiments, Met is selected from Ir, Pt, Os, Cu, and Zn. In some embodiments, the metal complex is + For the / Fc couple, it has a minimum oxidation potential of less than about 0.6 V in solution.

[0299] In some embodiments, the HIL / HTL material is selected from the group consisting of phthalocyanine and porphyrin compounds, starburst triarylamines, CFx fluorohydrocarbon polymers, conductive polymers (e.g., PEDOT:PSS, polyaniline, polythiophene), phosphonic acid and silane SAMs, triarylamine or polythiophene polymers with conductive dopants, organic compounds with conductive inorganic compounds (e.g., molybdenum and tungsten oxides), n-type semiconducting organic complexes, metal organometallic complexes, crosslinkable compounds, polythiophene-based polymers and copolymers, triarylamines, triarylamines with spirofluorene cores, arylamine carbazole compounds, triarylamines with (di)benzothiophene / (di)benzofuran, indolocarbazoles, isoindole compounds, and metal carbene complexes.

[0300] c) EBL: An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than one or more emitters closest to the EBL interface. In some embodiments, the compound used in the EBL comprises at least one carbazole group and / or at least one arylamine group. In some embodiments, the HOMO level of the compound used in the EBL is shallower than the HOMO level of one or more hosts in the EML. In some embodiments, the compound used in the EBL comprises the same molecule or the same functional group as used as one of the hosts described herein.

[0301] d) Host: The light-emitting layer of the organic EL device of the present disclosure preferably includes at least a light-emitting material as a dopant and a host material. The example of the host material is not particularly limited, and any metal complex or organic compound can be used as long as the host does not completely quench the light emission of the dopant.

[0302] Examples of metal complexes for use as hosts include those having the general formula: [ka] (wherein Met is a metal; Y 103 -Y 104 ) is a bidentate ligand, and Y 103 and Y 104 are independently selected from C, N, O, P, and S; 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal; and k'+k'' is the maximum number of ligands that can be bound to the metal.

[0303] In some embodiments, the metal complex is [ka] where (ON) is a bidentate ligand with the metal coordinated to atoms O and N.

[0304] In some embodiments, Met is selected from Ir and Pt. 103 -Y 104 ) is a carbene ligand.

[0305] In some embodiments, the host compound is selected from the group consisting of aromatic hydrocarbon ring compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazoline ... azole, 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, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-carbazole, aza-indolocarbazole, aza-triphenylene, aza-tetraphenylene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene; and 2 to 10 cyclic structural units of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, which 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 cyclic group. Each option within each group may be unsubstituted or substituted by the general substituents described herein, or may be further fused.

[0306] In some embodiments, the host compound is [ka] (In the formula, k is an integer of 0 to 20 or 1 to 20. X 101 ~X 108 is independently selected from C or N. 101 and Z 102 is independently selected from C, N, O, or S.

[0307] In some embodiments, the host material is selected from the group consisting of aryl carbazoles, metal 8-hydroxyquinolates (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorenes), aromatic fused rings, zinc complexes, chrysene-based compounds, aryl triphenylene compounds, poly-fused heteroaryl compounds, donor-acceptor type molecules, dibenzofuran / dibenzothiophene compounds, polymers (e.g., pvk), spirofluorene compounds, spirofluorene-carbazole compounds, indoloca compounds, and the like. The carbazoles, five-membered electron deficient heterocycles (e.g., triazoles, oxadiazoles), tetraphenylene complexes, metal phenoxypyridine compounds, metal coordination complexes (e.g., Zn, Al with N^N ligands), dibenzothiophene / dibenzofuran-carbazole compounds, silicon / germanium aryl compounds, aryl benzoyl esters, carbazoles linked by non-conjugated groups, aza-carbazole / dibenzofuran / dibenzothiophene compounds, and high triplet metal organometallic complexes (e.g., metal-carbene complexes).

[0308] e) Emitter materials in the EML: One or more emitter materials can be used with the compounds or devices of the present disclosure. The emitter materials can be emissive or non-emissive in the current device as described herein. The examples of emitter materials are not particularly limited, and any compound can be used as long as it can generate emission in a typical OLED device. Examples of suitable emitter materials include, but are not limited to, compounds that can generate emission via phosphorescence, non-delayed fluorescence, delayed fluorescence, especially thermally activated delayed fluorescence, i.e., TADF (also called E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0309] In some embodiments, the phosphor material is M(L 1 ) x (L 2 ) y (L 3 ) z having the formula: In the formula, L 1 , L 2 , and L 3 may be the same or different; x is 1, 2, or 3; y is 0, 1, or 2; z is 0, 1, or 2; x+y+z is the oxidation state of the metal M; L 1 is the structure of the ligand list: [ka] [ka] is selected from the group consisting of Each L 2 and L 3 is, independently, [ka] and the structures in the Ligand List; M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu; T is selected from the group consisting of B, Al, Ga, and In; K 1’ is a direct bond or NR e , P.R. e , O, S, and Se; Each Y 1 ~Y 15 is independently selected from the group consisting of carbon and nitrogen; Y' is BR e , N.R. e , P.R. e , O, S, Se, C=O, S=O, SO2, CR e R f , SiR e R f , and G e R e R f selected from the group consisting of; Each R a , R b , R c , and R d can independently represent one substitution up to the maximum possible number of substitutions, or no substitution; Each R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e , and R f is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and Any two substituents can be fused or linked to form a ring or to form a multidentate ligand.

[0310] In some embodiments, the emitter material comprises one or more of the following dopants from dopant group 1: [ka] [ka] [ka] [ka] is selected from the group consisting of Where: X 96 ~X 99 each is independently C or N; Each Y 100 is independently selected from the group consisting of NR″, O, S, and Se; R 10a , R 20a , R 30a , R 40a , and R 50a each independently represents one substitution, up to one substitution, or no substitution; R, R', R'', R 10a , R 11a , R 12a , R 13a , R 20a , R 30a , R 40a , R 50a , R 60 , R 70 , R 97 , R 98 , and R 99 Each of is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents can be joined or fused to form a ring.

[0311] In some embodiments, the emitter material comprises one or more of the following dopants from dopant group 2: [ka] [ka] [ka] [ka] [ka] [ka] is selected from the group consisting of Where: Each Y 100 is independently selected from the group consisting of NR″, O, S, and Se; L is independently selected from the group consisting of a direct bond, BR'', BR''R''', NR'', PR'', O, S, Se, C=O, C=S, C=Se, C=NR'', C=CR''R''', S=O, SO2, CR'', CR''R''', SiR''R'''', GeR''R'''', alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; X 100 and X 200 is selected for each occurrence from the group consisting of O, S, Se, NR'', and CR''R''''; Each R A’’ , R B’’ , R C’’ , R D’’ , R E’’ , and R F’’ independently represent monosubstitution, up to substitution, or no substitution; R, R', R'', R''', R A1’ , R A2’ , R A’’ , R B’’ , R C’’ , R D’’ , R E’’ , R F’’ , R G’’ , R H’’ , R I’’ , R J’’ , R K’’ , R L’’ , R M’’ , and R N’’ Each of is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents can be joined or fused to form a ring.

[0312] In some embodiments of the above dopant groups 1 and 2, each unsubstituted aromatic carbon atom can be replaced with N to form an azacycle. In some embodiments, the maximum number of N atoms in a ring is 1 or 2. In some embodiments of the above dopant group 2, the Pt atom in each formula can be replaced with a Pd atom.

[0313] In some embodiments of the OLED, the delayed fluorescent material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescent material is a metal complex. In some embodiments, the delayed fluorescent material is a non-metal complex. In some embodiments, the delayed fluorescent material is a Zn, Cu, Ag or Au complex.

[0314] In some embodiments of the OLED, the delayed fluorescent material is M(L 5 )(L 6 wherein M is Cu, Ag or Au; 5 and L 6 is different and L 5 and L 6 is independently [ka] [ka] selected from the group consisting of; A 1 ~A 9 are each independently selected from C or N; Each R P , R Q , and R U independently represent monosubstitution, up to substitution, or no substitution; Each R P , R Q , R U , R SA , R SB , R RA , R RB , R RC , R RD , R RE , and R RFare independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents can be joined or fused to form a ring.

[0315] In some embodiments of the OLED, the delayed fluorescent material is [ka] and wherein the donor moiety is selected from the group consisting of: Here, Y T , Y U , Y V and Y W are each independently selected from the group consisting of B, C, Si, Ge, N, P, O, S, Se, C=O, S=O, and SO2.

[0316] In some of the above embodiments, carbon ring atoms can be replaced with N, up to a total of three, along with their substituents, in each phenyl ring of any of the above structures.

[0317] In some embodiments, the delayed fluorescent material comprises at least one acceptor moiety selected from the group consisting of nitrile, isonitrile, borane, fluoride, pyridine, pyrimidine, pyrazine, triazine, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole, and oxadiazole. In some embodiments, the acceptor moiety and the donor moiety described herein are connected via a conjugated linker or sp 3 The connection can be directly through a non-conjugated linker, such as a carbon or silicon atom.

[0318] In some embodiments, the fluorescent material is: [ka] [ka] at least one chemical moiety selected from the group consisting of: Here, Y F , Y G , Y H , and Y I are each independently selected from the group consisting of B, C, Si, Ge, N, P, O, S, Se, C=O, S=O, and SO2; X F and X G are each independently selected from the group consisting of C and N.

[0319] In some of the above embodiments, carbon ring atoms can be replaced with N, up to a total of three, along with their substituents, in each phenyl ring of any of the above structures.

[0320] f)HBL: A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in significantly higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. A blocking layer can also be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and / or a higher triplet energy than one or more of the emitters closest to the HBL interface.

[0321] In some embodiments, the compounds used in the HBL contain the same molecules or the same functional groups as those used as the hosts described above.

[0322] In some embodiments, the compound used in HBL is [ka] (In the formula, k is an integer of 1 to 20; L 101is another ligand, and k′ is an integer from 1 to 3.

[0323] g)ETL: The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as it is typically used to transport electrons.

[0324] In some embodiments, the compounds used in the ETL have the following moieties in the molecule: [ka] and fullerene; where k is an integer from 1 to 20, and X 101 ~X 108 is selected from C or N; Z 101 is selected from the group consisting of C, N, O, and S.

[0325] In some embodiments, the metal complex used in the ETL has the following general formula: [ka] (Wherein, (ON) or (NN) is a bidentate ligand having a metal coordinated to the atoms O, N or N,N; L 101 is another ligand; and k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal.

[0326] In some embodiments, the ETL material is selected from the group consisting of anthracene-benzimidazole compounds, azatriphenylene derivatives, anthracene-benzothiazole compounds, metal 8-hydroxyquinolates, metal hydroxybenzoquinolates, bathocuproine compounds, 5-membered electron deficient heterocycles (e.g., triazoles, oxadiazoles, imidazoles, benzimidazoles), silole compounds, arylborane compounds, fluorinated aromatic compounds, fullerenes (e.g., C60), triazine complexes, and Zn(N̂N) complexes.

[0327] h) Charge Generation Layer (CGL) In tandem or stacked OLEDs, the CGL plays an important role in performance and consists of n-doped and p-doped layers for the injection of electrons and holes, respectively. The electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are replenished by electrons and holes injected from the cathode and anode, respectively, and then the bipolar current gradually reaches a steady state. Typical CGL materials contain n-type and p-type conductive dopants used in the transport layers.

[0328] In any compound disclosed herein, hydrogen atoms may be partially or fully deuterated. The minimum amount of hydrogen in a compound that is deuterated is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. As used herein, percent deuteration has its usual meaning and includes the percent of all possible hydrogen and deuterium atoms that are replaced by deuterium atoms. In some embodiments, the deuterium atom is bonded to an aromatic ring. In some embodiments, the deuterium atom is bonded to a saturated carbon atom, such as an alkyl or cycloalkyl carbon atom. In some other embodiments, the deuterium atom is bonded to a heteroatom, such as a Si or Ge atom.

[0329] It is understood that the various embodiments described herein are merely exemplary and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. Thus, the invention as claimed may include variations from the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It is understood that the various theories of why the invention works are not intended to be limiting.

[0330] E. Experimental Data Material synthesis Synthesis of 3,5-diisopropyl-N-(2-methyl-6-nitrophenyl)-[1,1'-biphenyl]-4-amine [ka]

[0331] In a 1 L round bottom flask, a solution of 3,5-diisopropyl-[1,1'-biphenyl]-4-amine (30.6 g, 1.00 equiv, 100 mmol) and 2-fluoro-1-methyl-3-nitrobenzene (25.3 g, 1.61 equiv, 161 mmol) in anhydrous tetrahydrofuran (THF) (350 mL) was prepared under nitrogen. The mixture was then cooled to 0° C. using an ice bath for 15 min. A solution of lithium diisopropylamide (LDA) (134 mL, 1.98 mol, 2.65 equiv, 266 mmol) was added dropwise over 85 min. The temperature (external) was maintained below 1° C. during the addition of LDA. The resulting dark purple solution was stirred and allowed to warm slowly to 20° C. over 20 h under a positive pressure of nitrogen. An aliquot was taken after 20 h. The reaction mixture was cooled briefly in an ice bath and carefully diluted with brine (200 mL) and ethyl acetate (EtOAc) (200 mL) and stirred for 1.5 h. The mixture was filtered through a wide plug of Celite (<5.5 in. wide x <2.0 in. long) and washed with 100 mL of brine and then 1.2 L of EtOAc until the filtrate was nearly colorless. The aqueous layer was further extracted with dichloromethane (DCM) (2 x 150 mL) and the combined organics were dried over MgSO4 for several hours. The resulting mixture was then filtered through a short pad of silica and then washed with DCM until the filtrate was nearly colorless. The product was concentrated under vacuum at 45°C to give a dark brown semi-solid and then dried overnight under house vacuum. Over 60 g of a dark brown solid was obtained. The solid was diluted with 100 mL of dichloromethane and loaded onto a silica gel plug as a suspension with some additional dichloromethane and then eluted with 100% heptane to 10% EtOAc / heptane. The product was concentrated under vacuum at 45° C. to give a thick paste, which was suspended in n-hexane (60 mL) and methanol (MeOH) (200 mL), then gently capped and vigorously stirred at room temperature (ca. 22° C.) for more than 40 h. The suspension was filtered and the solid was washed with MeOH (4×40 mL) and dried in air for several hours. 3,5-Diisopropyl-N-(2-methyl-6-nitrophenyl)-[1,1′-biphenyl]-4-amine (1) was obtained as a brown powder, 23.0 g (58% yield). [ka]

[0332] N 1 Synthesis of -(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-6-methylbenzene-1,2-diamine

[0333] Acetic acid (150 mL) and saturated aqueous NH4Cl (60 mL) were added to a solution of 3,5-diisopropyl-N-(2-methyl-6-nitrophenyl)-[1,1'-biphenyl]-4-amine (compound 1) (14.3 g, 1.00 equiv., 35.7 mmol) in tetrahydrofuran (THF) (300 mL) in a 1 L round bottom flask under air. The resulting brown suspension was stirred vigorously for 15 min at 0°C. Zinc powder (14.2 g, 6.00 equiv., 214 mmol) was then added in one portion. The resulting dark mixture was capped with a septum and fitted with an air vent needle, and the mixture was then stirred at 0°C for 1.5 h. After 1.5 h, another portion of zinc was added (7.10 g, 3.00 equiv.) and the product was stirred for 1 h. After stirring, saturated aqueous NH4Cl (15.00 mL) and zinc (4.70 g, 2.00 equiv.) were added and the resulting mixture was stirred for an additional 1 h.

[0334] An aliquot was partitioned between aqueous Na2CO3 / EtOAc and then analyzed by thin layer chromatography (TLC) (10% EtOAc / heptane), which showed complete conversion of the starting material. It was filtered through a short pad of Celite and then washed with EtOAc (300 mL). The product was concentrated under vacuum up to 52 °C to give a purple residue and then stored in the freezer overnight. The next day, the product was suspended in EtOAc (400 mL) and aqueous Na2CO3 (350 mL) was carefully added and stirred until bubbling ceased (approximately 20 min). The product was filtered through a wide pad of Celite (5.50 in. wide x 0.75 in. long) to remove insoluble white salts, which was washed with EtOAc (300 mL) / deionized (DI) water (150 mL) and then additional EtOAc (200 mL). The phases were separated and the extraction was repeated with EtOAc (150 mL). The combined organics were dried over MgSO4, filtered, and then concentrated under vacuum at 45°C. The resulting maroon syrup was diluted with dichloromethane, loaded onto a silica gel column, and eluted with 100% heptane to 10% EtOAc / heptane. The product was concentrated under vacuum at 45°C to give compound 2 as a dark maroon semi-solid, which was briefly dried under house vacuum. The resulting compound 2 (13.7 g) was estimated to be 80% pure (86% yield) and was used directly in the next step without further purification.

[0335] Synthesis of 1-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-7-methyl-2-(phenanthro[3,2-b]benzofuran-11-yl)-1H-benzo[d]imidazole (4) [ka]

[0336] A 1 L round bottom flask containing N1-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-6-methylbenzene-1,2-diamine (2) (13.7 g, 1.18 equiv., 30.6 mmol) was fitted with a reflux condenser and then the solid reagents: phenanthro[3,2-b]benzofuran-11-carbaldehyde 3 (7.80 g, 1.00 equiv., 25.8 mmol) and sodium bisulfite (1.91 g, 2.00 equiv., 18.3 mmol) were added, followed by dimethylformamide (DMF) (400 mL). The reaction mixture was stirred vigorously at 135 °C (preheated oil bath) in open air for 47 h. TLC (20% EtOAc / heptane) showed complete conversion of starting material and formation of a major product spot that was dark blue in the UV. The product was allowed to cool slowly over 47 h and stirred in open air overnight. The next day, most of the DMF was removed under vacuum at 67-72°C. The residue was diluted with EtOAc (500 mL), DI water (100 mL), and brine (100 mL) and then shaken to dissolve all solids. The phases were separated and the organics were washed with brine (3 x 120 mL) and then dried briefly over MgSO4. The product was filtered and then concentrated under vacuum at 45°C to give a dark purple foam. The product was dissolved in dichloromethane and loaded onto a silica gel column (2.0" wide x 8.0" long) and then eluted with 100% heptane to 5% EtOAc / heptane to remove colored non-polar impurities. The elution was continued and completed with 15% to 20% EtOAc / heptane. The resulting fractions were concentrated under vacuum at 45°C, then the residue was diluted with heptane (20 mL) and then methanol (MeOH) (125 mL) and stirred vigorously at room temperature for 14 hours. After 14 hours, the suspension was filtered, washed with heptane (40 mL), then MeOH (3 x 20 mL), and then dried in air to give 27.3 g of a grey solid. The resulting solid was dissolved in warm dichloromethane (60 mL) and then cooled. MeOH (240 mL) was added slowly to form a light precipitate. The resulting suspension was gently capped and vigorously stirred at room temperature for 2 hours. The product was filtered, washed with 10% dichloromethane in MeOH (50 mL), then MeOH (50 mL), and then dried in air. An off-white beige / khaki solid (25.8 g) was obtained.TLC showed that the product was not pure. Therefore, the solid was dissolved in hot dichloromethane (60 mL) and then cooled. MeOH (160 mL) was added slowly, resulting in the formation of a light precipitate. Persistent turbidity began to form after the first 70 mL of methanol was added. The resulting suspension was gently capped and vigorously stirred at room temperature for 2 h. The product was then filtered, washed with 10% dichloromethane in MeOH (50 mL), then MeOH (2×50 mL), and dried in air. Compound 4 was obtained as an off-white crystalline solid (21.6 g, estimated yield 74%).

[0337] Synthesis of 1-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-7-(methyl-d3)-2-(phenanthro[3,2-b]benzofuran-11-yl)-1H-benzo[d]imidazole (5) [ka]

[0338] A 250 mL 4-neck flask was charged with 1-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-7-methyl-2-(phenanthro[3,2-b]benzofuran-11-yl)-1H-benzo[d]imidazole (compound 4) (3.1 g, 4.9 mmol, 1.0 equiv.) and dimethylsulfoxide-d6 (98 mL). Potassium tert-butoxide (550 mg, 4.9 mmol, 1.0 equiv.) was added and the reaction mixture was then heated at 95° C. for 16 hours. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate (300 mL) and water (400 mL). The layers were separated and the aqueous layer was extracted with ethyl acetate (2×200 mL). The combined organic layers were dried over sodium sulfate, then filtered and concentrated under reduced pressure to form a dark oil. The dark oil was dissolved in a minimum amount of dichloromethane and purified on a Biotage automated chromatography system (three stacked 330 g silica gel cartridges) eluted with a gradient of 0% to 10% ethyl acetate in hexanes. The above procedure was repeated two more times to give 1-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-7-(methyl-d3)-2-(phenanthro[3,2-b]benzofuran-11-yl)-1H-benzo[d]imidazole (compound 5) (600 mg, 20% yield) as a pale yellow solid.

[0339] Synthesis of bis[4-(tert-butyl)-(2-phen-2'-yl)pyridin-1-yl]-[3-(3,5-diisopropyl)-[1,1'-biphenyl]-4-yl)-4-(methyl-d3)-(2-(phenanthro[3,2-b]benzofuran-11-yl)-10'-yl)-1H-benzo[d]imidazol-1-yl]iridium(III) (compound 1 of the present invention). [ka]

[0340] A 250 mL 4-neck flask equipped with a stir bar and condenser was charged with [Ir(4-(tert-butyl)-(2-phenyl-2'-yl)pyridin-1-yl)(-1H))2(MeOH)2]trifluoromethane-sulfonate (842 mg, 1.02 mmol, 1.0 equiv.), 1-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-7-(methyl-d3)-2-(phenanthro[3,2-b]benzofuran-11-yl)-1H-benzo[d]imidazole (compound 5) (650 mg, 1.02 mmol, 1.0 equiv.), and 2-ethoxyethanol (50 mL). The mixture was sparged with nitrogen for several minutes. 2,6-Lutidine (218 mg, 2.04 mmol, 2.0 equiv) was added to the mixture and the reaction mixture was heated at 120 °C for 16 h. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. The residue was dissolved in a minimum amount of dichloromethane and loaded onto a Biotage automated chromatography system (6-stacked 120 g Sorbtech silica gel cartridges) and eluted with a gradient of 1-12% acetone in hexanes. The pure product fractions were concentrated under reduced pressure. The resulting material was dissolved in dichloromethane (50 mL), precipitated with methanol (100 mL), and then filtered. The resulting solid was washed with methanol (100 mL) and then dried overnight at 65° C. in a vacuum oven to give bis[4-(tert-butyl)-(2-phen-2′-yl)pyridin-1-yl]-[3-(3,5-diisopropyl)-[1,1′-biphenyl]-4-yl)-4-(methyl-d3)-(2-(phenanthro[3,2-b]benzofuran-11-yl)-10′-yl)-1H-benzo[d]imidazol-1-yl]iridium(III) (compound 1 of the present invention) (300 mg, 23% yield) as a yellow solid. [ka]

[0341] Compound A1 can be prepared by a method similar to that reported in J. Org. Chem. 2013, 78, 4649 for the C-N coupling of hindered aryl halides.

[0342] A flask is charged with Pd2(dba)3 (0.02 equiv.), trineopentylphosphine (0.04 equiv.), sodium tert-butoxide (1.5 equiv.), aryl bromide (1 equiv.), arylamine (1.2 equiv.), and toluene to achieve a concentration of 0.5 M relative to the aryl bromide. The mixture is purged with nitrogen and then heated at 80 °C for 24 h. The reaction mixture is diluted with ethyl acetate, filtered through a pad of Celite®, and concentrated to dryness on a rotary evaporator. The crude residue is then purified by column chromatography using silica gel as the stationary phase and 0.50-10% ethyl acetate in hexane as the eluent. [ka]

[0343] This reduction can be carried out in a manner similar to the conversion of compound 1 to compound 2 using zinc metal, acetic acid, and ammonium chloride in THF as shown above. [ka]

[0344] This condensation can be carried out in a manner similar to the conversion of compound 3 to compound 4 using zinc metal, acetic acid, and ammonium chloride in THF as shown above.

[0345] Compound A3 can then be used to synthesize other L-type compounds in the manner described above or in the applications incorporated herein by reference. B It can be coupled with a ligand to produce the desired compound.

[0346] Other L-type compounds similar to compounds 4 and A3, including polycyclic fused ring systems, A Ligands can be made using similar techniques and then fused to different L B Upon coupling with ligands, a variety of compounds of the invention can be prepared.

[0347] Device Examples All example devices were placed in high vacuum (<10 -7 The devices were fabricated by thermal evaporation at 3700 Å (1000 Torr). The anode electrode was 800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of Liq (lithium 8-hydroxyquinoline) and 1,000 Å of Al. All devices were encapsulated with a glass lid sealed with epoxy resin in a nitrogen glove box (<1 ppm H2O and O2) immediately after fabrication, and a moisture getter was incorporated within the package. The organic stack of the example device consisted of, from the ITO surface, 100 Å of LG101 (purchased from LG Chem) as a hole injection layer (HIL); 400 Å of HTM as a hole transport layer (HTL); 400 Å thick light emitting layer (EML); 50 Å of EBM as an electron blocking layer (EBL); an emissive layer containing H-host (H1):E-host (H2) in a 7:3 ratio and 5 wt% green emitter; and 300 Å of Liq (8-hydroxyquinoline lithium) doped with 35% ETM as an ETL. The chemical structures of the device materials are shown below. [ka]

[0348] The device structure is shown in Table 2. [Table 2] [Table 3]

[0349] Table 3 provides a summary of the electroluminescent device performance of the materials. The data shows that the introduction of deuterated methyl on the benzimidazole results in a hypsochromic shift of 3 nm from 530 nm for the comparative compound to 527 nm for the inventive compound. As background information, the ideal peak wavelength for use in OLEDs is bluer than 530 nm. It is also noteworthy that the inventive compound shows a better FWHM of 27 nm versus 28 nm for the comparative compound. This hypsochromic shift exceeds any value that may be attributable to experimental error, and the observed improvement is significant and unexpected.

Claims

1. Formula Ir(L Ａ ) ｘ (L Ｂ ) ｙ (L Ｃ ) ｚ A compound of the formula: x is 1 or 2; y is 1 or 2; z is 0 or 1; and x+y+z=3; The first ligand L Ａ is represented by formula I 【Chemistry 1】 The structure includes Ligand L Ｂ is represented by formula II 【Chemistry 2】 The structure includes Ligand L Ｃ is a bidentate ligand; Moiety B is a polycyclic fused ring system containing at least four rings, each ring of the polycyclic fused ring system being independently a 5- to 10-membered carbocyclic or heterocyclic ring; each of moieties C and D is independently a monocyclic ring or a polycyclic fused ring system, each ring of the monocyclic ring or polycyclic fused ring system is independently a 5-10 membered, carbocyclic or heterocyclic ring; X １ ~X ４ and Z １ ~Z ６ each is independently C or N; L ０ is 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, SO ２ , CRR′, SiRR′, GeRR′, and combinations thereof; Y Ａ BR Ｎ , N.R. Ｎ , P.R. Ｎ , O, S, Se, C=O, S=O, SO ２ , CRR′, SiRR′, and GeRR′; R Ａ , R Ｂ , R Ｃ , and R Ｄ each independently represents from one substitution up to the maximum allowed substitution, or no substitution; Each R, R', R Ａ , R Ｂ , R Ｃ , R Ｄ , and R Ｎ is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; any two substituents may be joined or fused to form a ring; and At least two R Ａ The substituents may be linked to form a ring or may be linked to at least one R Ａ is not hydrogen, except that 【Chemistry 3】 provided that the compound is not.

2. Moiety B is a polycyclic fused ring system containing at least five rings, moiety B includes moiety B1 and moiety B2, moiety B1 includes Z １ and Z ２ and moiety B2 is fused to moiety B1, each of moieties B1 and B2 being an independently selected monocyclic ring or polycyclic fused ring system, each ring of the monocyclic ring or polycyclic fused ring system being independently a 5-10 membered carbocyclic or heterocyclic ring; and / or each of moieties B1 and B2 being independently selected 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, ...benzo 2. The compound of claim 1, wherein the compound is selected from the group consisting of azothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole derived carbene, aza-benzimidazole derived carbene, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.

3. each of moieties C and D is independently selected from benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, 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, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene; and / or L ０ is a direct bond, BR, NR, or PR; and / or Y Ａ O, S, Se, BR Ｎ , N.R. Ｎ , or PR Ｎ and / or R Ｎ 2. The compound of claim 1, wherein comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof.

4. At least one R Ａ contains a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or at least one R Ｂ contains a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or at least one R Ｃ contains a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or at least one R Ｄ 2. The compound of claim 1, wherein comprises a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and electron-withdrawing groups of the EWG1 list defined herein.

5. Two adjacent R Ａ is attached or fused to form a moiety A1, said moiety being a monocyclic ring or a polycyclic fused ring system, each ring of said monocyclic ring or said polycyclic fused ring system being independently a 5-10 membered carbocyclic or heterocyclic ring.

6. The ligand L Ａ is selected from the group consisting of the structures of List 4 defined herein, wherein: X ５ ~X ３０ each is independently C or N; Y Ｂ and Y Ｃ Each of the groups independently represents BR ｅ , N.R. ｅ , P.R. ｅ , O, S, Se, C=O, S=O, SO ２ , C.R. ｅ R ｆ , SiR ｅ R ｆ , and GeR ｅ R ｆ selected from the group consisting of: R Ａ１ represents one substitution up to the maximum number of possible substitutions; Each R Ａ , R Ｂ１ , R Ｂ２ , and R Ｂ３ independently represent one substitution up to the maximum possible number of substitutions, or no substitution; Each R ｅ , R ｆ , R Ａ , R Ａ１ , R Ｂ１ , R Ｂ２ , and R Ｂ３ are independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; The remaining variables are the same as previously defined; If present, at least one R Ａ１ is not hydrogen; and 2. The compound of claim 1, wherein any two adjacent substituents can be fused or linked to form a ring or to form a multidentate ligand.

7. The ligand L Ａ is selected from the group consisting of the structures of List 5 defined herein, wherein: Y Ｂ and Y Ｃ Each of the groups independently represents BR ｅ , N.R. ｅ , P.R. ｅ , O, S, Se, C=O, S=O, SO ２ , C.R. ｅ R ｆ , SiR ｅ R ｆ , and GeR ｅ R ｆ selected from the group consisting of: R Ａ１ represents one substitution up to the maximum number of possible substitutions; Each R Ａ , R Ａ１ , R Ｂ１ , R Ｂ２ and R Ｂ３ independently represent one substitution up to the maximum possible number of substitutions, or no substitution; Each R ｅ , R ｆ , R Ａ , R Ａ１ , R Ｂ１ , R Ｂ２ , R Ｂ３ , R ｅ , and R ｆ are independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; At least one R Ａ１ is not hydrogen; The remaining variables are the same as previously defined; and 2. The compound of claim 1, wherein any two adjacent substituents can be fused or linked to form a ring or to form a multidentate ligand.

8. The ligand L Ａ But, L Ａｉ (R Ｊ ) (R Ｋ ) (R Ｌ ) (Y Ｍ ), L Ａｉ’ (R Ｊ ) (R Ｋ ) (R Ｌ ) (Y Ｍ ) (Y Ｎ ), L Ａ’ｉ’’ (R Ｊ ) (R Ｋ ) (R Ｌ ) (Y Ｍ ), L Ａ’ｉ’’’ (R Ｊ ) (R Ｋ ) (R Ｌ ) (Y Ｍ ) (Y Ｎ ) are selected from In the formula, i is an integer from 1 to 21, i' is an integer from 13 to 26, i'' is an integer from 1 to 38, and i''' is an integer from 39 to 80; R Ｊ , R Ｋ , and R Ｌ are each independently selected from R1 to R411; Ｋ’ is selected from R2 to R411; and Y Ｍ and Y Ｎ each is independently selected from Y1-Y50; In the ceremony, L Ａ 1-(R1)(R1)(R1)(Y1)~L Ａ 26-(R411)(R411)(R411)(Y50)(Y50) each have the structure defined in List 6 defined herein; In the ceremony, L Ａ’ 1-(R1)(R2)(R1)(Y1)~L Ａ’ 80-(R411)(R411)(R411)(Y50)(Y50) each have the structure defined in List 7 defined herein; wherein R1 to R411 have the structures shown in List 8 as defined herein; and 2. The compound of claim 1, wherein Y1-Y50 have the structures shown in List 9 as defined herein.

9. L Ｂ is selected from the group consisting of the structures of List 10 defined herein; and L Ｃ But List 10 and 【Chemistry 4】 is selected from the group consisting of During the ceremony, T is selected from the group consisting of B, Al, Ga, and In; K １’ is a single bond, O, S, NR ｅ , P.R. ｅ , B.R. ｅ , C.R. ｅ R ｆ , and SiR ｅ R ｆ selected from the group consisting of: Y １ ~Y １３ each is independently selected from the group consisting of C and N; Y' is BR ｅ , B.R. ｅ R ｆ , N.R. ｅ , P.R. ｅ , P(O)R ｅ , O, S, Se, C=O, C=S, C=Se, C=NR ｅ , C=CR ｅ R ｆ , S=O, SO ２ , C.R. ｅ R ｆ , SiR ｅ R ｆ , and GeR ｅ R ｆ selected from the group consisting of: R ｅ and R ｆ can be fused or linked to form a ring; Each R ａ , R ｂ , R ｃ , and R ｄ independently represent one substitution up to the maximum permitted number of substitutions, or no substitution; R ａ１ , R ｂ１ , R ｃ１ , R ｄ１ , R ａ , R ｂ , R ｃ , R ｄ , R ｅ , and R ｆ each is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and R ａ１ , R ｂ１ , R ｃ１ , R ｄ１ , R ａ , R ｂ , R ｃ , and R ｄ 2. The compound of claim 1, wherein any two of the substituents of can be fused or linked to form a ring or to form a multidentate ligand.

10. Formula Ir(L Ａ )(L Ｂｋ ), formula Ir(L ２ )(L Ａ ), formula Ir(L ２ )(L Ｂｋ ), or Ir(L Ａ )(L ２ )(L Ｃ )(L Ａ )(L Ｂｋ )(L Ｃ ), having In the ceremony, L Ａ L Ａ 1-(R1)(R1)(R1)(Y1)~L Ａ 21-(R411)(R411)(R411)(Y50), L Ａ 22-(R1)(R1)(R1)(Y1)(Y1)~L Ａ 64-(R411)(R411)(R411)(Y50)(Y50), L Ａ’ 1-(R1)(R2)(R1)(Y1)~L Ａ’ 38-(R411)(R411)(R411)(Y50), and L Ａ’ 39-(R1)(R2)(R1)(Y1)(Y1)~L Ａ’ 78-(R411)(R411)(R411)(Y50)(Y50); In the formula, k is an integer from 1 to 530, and each L Ｂｋ has the structure defined in Listing 12 as defined herein; In the formula, each L Ｃｊ－Ｉ is the formula 【Chemistry 5】 and Each L Ｃｊ－ＩＩ is the formula 【Chemistry 6】 and L Ｃｊ－Ｉ and L Ｃｊ－ＩＩ Each L Ｃｊ About R ２０１ and R ２０２ are each independently defined in List 13 as defined herein; R Ｄ１ ~R Ｄ２４６ The compound of claim 1 having the structure of List 14 as defined herein.

11. 2. The compound of claim 1, selected from the group consisting of the structures of list 16 defined herein.

12. anode; A cathode; and An organic layer disposed between the anode and the cathode 13. An organic light emitting device (OLED) comprising:

13. anode; A cathode; and An organic layer disposed between the anode and the cathode 13. A consumer product comprising an organic light emitting device (OLED) comprising:

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