Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. Provided herein is a compound of formula Ir (LA) x (LB) y comprising a structure of formula I. In Formula I, each of x and y is independently 1 or 2, and x + y = 3; each of X1 to X17 is C or N; each R1, R2, R3, R4, RA, RB, RC, RD and RE is hydrogen or a universal substituent as defined herein; at least one of R1 to R4 is not hydrogen, deuterium or halogen; and a combination of a pair of R1 or R2 and a pair of R3 or R4 has a greater combined Van der Waals surface area (Van der Waals surface area), and one of the pairs has a taper angle of at least a target taper angle, where the target taper angle is 35 degrees. Formulations, OLEDs, and consumer products containing the compounds are also provided.

Description

[0001] Cross Reference to Related Applications

[0002] This application is a continuation-in-part of co-pending U.S. Patent Application No. 18 / 814,301 filed August 23, 2024, and U.S. Patent Application No. 19 / 176,025 filed April 10, 2025. This application also claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 63 / 671,920 filed July 16, 2024, the entire contents of all of the above-referenced applications are incorporated herein by reference. TECHNICAL FIELD

[0003] The present disclosure relates generally to organic or metal-coordination compounds and formulations and various uses thereof, including as emitters, sensitizers, charge transporters, or exciton transporters in devices such as organic light emitting diodes and related electronic devices and consumer products. BACKGROUND

[0004] Opto-electronic devices that make use of organic materials are becoming increasingly important for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential to be lower cost than alternative devices that use inorganic materials. In addition, the inherent properties of organic materials, such as their flexibility, can make them well suited for particular applications, such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, organic

[0005] OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in the

[0006] One application for emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors (known as "saturated" colors). Specifically, such standards call for saturated red, green, and blue pixels. Alternatively, an OLED can be designed to emit white light. In conventional liquid crystal displays, color is achieved by the use of absorptive filters. The same technique can be used with OLEDs. White SUMMARY

[0007] In one aspect, the present disclosure provides a compound of formula Ir(L A ) x (L B )y a compound comprising Formula I wherein:

[0008] each of x and y is independently 1 or 2, and x+y = 3;

[0009] X 1 to X 17 each independently is C or N;

[0010] R A , R B , R C , R D , and R E each independently represents single substitution to the maximum allowable substitution or no substitution;

[0011] each R 1 , R 2 , R 3 , R 4 , R A , R B , R C , R D , and R E is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof;

[0012] any two substituents can be joined or fused to form a ring;

[0013] at least one of R 1 , R 2 , R 3 , or R 4 is not hydrogen, deuterium, or halogen;

[0014] each of R 1 , R 2 , R 3 , and R 4 has a corresponding cone angle R 1 (CA), R 2 (CA), R 3 (CA), and R 4 (CA);

[0015] R 1 , R 2 , R 3 , and R 4Each of them has a corresponding van der Waals surface area R. 1 (VdW), R 2 (VdW), R 3 (VdW) and R 4 (VdW); and

[0016] At least one of the following is true:

[0017] (i) And R 1 (CA) or R 3 At least one of (CA) is greater than or equal to the target cone angle.

[0018] (ii) And R 1 (CA) or R 4 At least one of (CA) is greater than or equal to the target cone angle.

[0019] (iii) And R 2 (CA) or R 3 At least one of (CA) is greater than or equal to the target cone angle, or

[0020] (iv) And R 2 (CA) or R 4 At least one of (CA) is greater than or equal to the target cone angle;

[0021] The target cone angle is 35 degrees.

[0022] In another aspect, this disclosure provides a formulation comprising the formula Ir(L) as described herein. A ) x (L B ) y Compounds.

[0023] In another aspect, this disclosure provides an OLED having Ir(L) as described herein. A ) x (L B ) y The organic layer of the compound.

[0024] In another aspect, this disclosure provides a consumer product comprising an OLED having an organic layer comprising Ir(L) as described herein. A ) x (L B ) y Compounds. Attached Figure Description

[0025] Figure 1 An organic light-emitting device is shown.

[0026] Figure 2 An inverted organic light-emitting device without an independent electron transport layer is demonstrated. Detailed Implementation

[0027] A. Terminology

[0028] Unless otherwise specified, the following terms as used herein are defined as follows:

[0029] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. When the first layer is described as being "placed" "above" the second layer, the first layer is placed further away from the substrate. Unless specified that the first layer "contacts" the second layer, other layers may exist between the first and second layers. For example, even if various organic layers exist between the cathode and anode, the cathode may still be described as being "placed" "above" the anode.

[0030] As used herein, “solution-handleable” means capable of dissolving, dispersing or transporting in and / or depositing from a liquid medium in the form of a solution or suspension.

[0031] As used herein, and as will generally be understood by those skilled in the art, if the first energy level is closer to the vacuum level, then the first "Highest Occupied Molecular Orbital" (HOMO) or "Lowest Unoccupied Molecular Orbital" (LUMO) level is "greater than" or "higher than" the second HOMO or LUMO level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO level corresponds to an IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). On a conventional energy level diagram with the vacuum level at the top, the LUMO levels of a material are higher than the HOMO levels of the same material. "Higher" HOMO or LUMO levels appear to be closer to the top of this diagram than "lower" HOMO or LUMO levels.

[0032] As used herein, and as will generally be understood by those skilled in the art, if the first work function has a higher absolute value, then the first work function is “greater” or “higher” than the second work function. This is because the work function is typically measured as a negative number relative to the vacuum level, meaning that the “higher” work function is more negative. On a conventional energy level diagram with the vacuum level at the top, the “higher” work function is illustrated as being farther from the vacuum level in the downward direction. Therefore, the definitions of HOMO and LUMO levels follow different rules than those for the work function.

[0033] This document may describe light emission regions by referring to the color of the light emitted by layers, materials, areas, and devices. Generally, as used herein, an emitting region that produces a particular color of light may include one or more emitting layers arranged in a stacked manner on top of each other.

[0034] As used herein, “NIR,” “red,” “green,” “blue,” and “yellow” layers, materials, regions, or devices refer to layers, materials, regions, or devices that emit light in the wavelength ranges of approximately 700–1500 nm, 580–700 nm, 500–600 nm, 400–500 nm, and 540–600 nm, respectively, or layers, materials, regions, or devices that have the highest emission spectral peak in the corresponding wavelength regions. In some arrangements, individual regions, layers, materials, or devices may provide separate “deep blue” and “light blue” emissions. As used herein, a “deep blue” emission component refers to an emission whose peak emission wavelength is at least approximately 4 nm smaller than the peak emission wavelength of the “light blue” emission component. Typically, the peak emission wavelength of the “light blue” emission component is in the range of approximately 465–500 nm, and the peak emission wavelength of the “deep blue” emission component is in the range of approximately 400–470 nm, but these ranges may vary for some configurations.

[0035] In some arrangements, a color-changing layer is provided that converts, modifies, or alters the color of light emitted by another layer to emit light with a different wavelength. This color-changing layer can be tuned to shift the wavelength of light emitted by the other layer by a defined amount, such as by the difference between the wavelength of the emitted light and the wavelength of the resulting light. Generally, there are two types of color-changing layers: color filters that modify the spectrum by removing light of unwanted wavelengths, and color-changing layers that convert higher-energy photons into lower-energy ones. For example, a "red" filter may be present to filter input light to remove light with wavelengths outside the range of approximately 580-700 nm. The component of "color" refers to the component of light that produces or otherwise emits a specific color as described above when activated or used. For example, "a first emission region of a first color" and "a second emission region of a second color different from the first color" describe two emission regions that emit two different colors as described above when activated within the device.

[0036] As used herein, the light initially generated by a material, layer, or region is the exact opposite of the light ultimately emitted by the same or different structures, allowing the emitting materials, layers, and regions to be distinguished from each other and from other structures. Initial light generation is typically a result of energy level changes that lead to photon emission. For example, an organic emitting material may initially produce blue light, which can be converted into red or green light by a color filter, quantum dot, or other structure, causing the entire emitting stack or subpixel to emit red or green light. In this case, the initial emitting material, region, or layer may be referred to as the "blue" component, even if the subpixel is the "red" or "green" component.

[0037] In some cases, the color of components, such as the color of emitting regions, subpixels, color-changing layers, etc., can preferably be described according to 1931 CIE coordinates. For example, a yellow emitting material may have multiple peak emission wavelengths, one in or near the edge of the "green" region and one in or near the edge of the "red" region, as previously described. Therefore, as used herein, each color item also corresponds to a shape in the 1931 CIE coordinate color space. The shape in the 1931 CIE color space is constructed by tracing the trajectory between two color points and any other interior points. For example, the interior shape parameters for red, green, blue, and yellow can be defined as follows:

[0038]

[0039] The terms “halogen,” “halogen,” and “halogen group” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0040] The term "acyl" refers to a substituted carbonyl group (-C(O)-R). s ).

[0041] The term "ester" refers to a substituted oxycarbonyl group (-OC(O)-R). s or -C(O)-OR s ) group.

[0042] The term "ether" refers to -OR s Group.

[0043] The terms "thio-" or "thioether" are used interchangeably and refer to -SR s Group.

[0044] The term "selenyl" refers to -SeR s Group.

[0045] The term "sulfinyl" refers to -S(O)-R s Group.

[0046] The term "sulfonyl" refers to -SO2-Rs Group.

[0047] The term "phosphono" refers to a group containing at least one phosphorus atom bonded to the relevant structure. Common examples of phosphono groups include, but are not limited to, -P(R) s )2 group or -PO(R s )2 groups, wherein each R s They can be the same or different.

[0048] The term "silyl group" refers to a group containing at least one silicon atom bonded to the relevant structure. Common examples of silyl groups include, but are not limited to, -Si(R s )3 groups, wherein each R s They can be the same or different.

[0049] The term "germanium alkyl" refers to a group containing at least one germanium atom bonded to the relevant structure. Common examples of germanium alkyl groups include, but are not limited to, -Ge(R s )3 groups, wherein each R s They can be the same or different.

[0050] The term "boronyl" refers to a group containing at least one boron atom bonded to the relevant structure. Common examples of boronyl groups include, but are not limited to, -B(R s )2 group or its Lewis adduct -B(R s )3 groups, of which R s They can be the same or different.

[0051] In each of the above, R s It can be hydrogen or a substituent selected from the group of general substituents as defined in this application. Preferred R s Selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. More preferably, R s Choose from the following groups: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0052] The term "alkyl" refers to and includes both straight-chain and branched alkyl groups having alkyl carbon atoms bonded to the relevant structure. Preferred alkyl groups are those containing one to fifteen carbon atoms, more preferably one to nine carbon atoms, and include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,3-dimethylpropyl, 1,1-dimethylpropyl, 2-ethylpropyl, 1,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, etc. In addition, alkyl groups can be further substituted.

[0053] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spirocyclic alkyl groups having cycloalkyl carbon atoms bonded to the relevant structure. Preferred cycloalkyl groups are those containing 3 to 12 cyclic carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. Furthermore, the cycloalkyl group may be further substituted.

[0054] The terms "heteroalkyl" or "heterocyclic alkyl" refer to an alkyl or cycloalkyl group having at least one carbon atom substituted with a heteroatom, respectively. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. Furthermore, the heteroalkyl or heterocyclic alkyl group may be further substituted.

[0055] The term "alkenyl" refers to and includes both straight-chain and branched olefin groups. An alkenyl is essentially an alkyl group comprising at least one carbon-carbon double bond in an alkyl chain, wherein one carbon atom originates from a carbon-carbon double bond bonded to the associated structure. A cycloalkenyl is essentially a cycloalkyl group comprising at least one carbon-carbon double bond in a cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group having at least one carbon atom substituted 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 two to fifteen carbon atoms. Furthermore, alkenyl, cycloalkenyl, or heteroalkenyl groups may be further substituted.

[0056] The term "alkynyl" refers to and includes both straight-chain and branched alkyne groups. An alkynyl group is essentially an alkyl group comprising at least one carbon-carbon triple bond in an alkyl chain, where one carbon atom originates from a carbon-carbon triple bond bonded to the relevant structure. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Furthermore, the alkynyl group may be further substituted.

[0057] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an aryl-substituted alkyl group having an alkyl carbon atom bonded to the relevant structure. Furthermore, aralkyl groups can be further substituted.

[0058] 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. The terms "heteroaromatic cyclic group" and "heteroaryl group" are used interchangeably. Preferred non-aromatic heterocyclic groups are those containing 3 to 10 ring atoms, preferably those containing 3 to 7 ring atoms including at least one heteroatom, and include cyclic amines such as morpholino, piperidinyl, pyrrolyl, etc., and cyclic ethers / thioethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. Furthermore, the heterocyclic group may be further substituted or fused.

[0059] The term "aryl" refers to and includes both monocyclic and polycyclic aromatic hydrocarbon groups. Polycyclic groups may have two or more rings, wherein two carbons are common to two adjacent rings (the rings are "fused"). Preferred aryl groups are those containing six to thirty carbon atoms, more preferably six to twenty-four carbon atoms, six to eighteen carbon atoms, and more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six, ten, twelve, fourteen, or eighteen carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, pyrene, etc. Perylene and azulene, preferably phenyl, biphenyl, biphenylene, triphenylene, and naphthalene. Additionally, the aryl group may be further substituted or fused, such as, but not limited to, fluorene.

[0060] The term "heteroaryl" refers to and includes both monocyclic aromatic groups and polycyclic aromatic ring systems having at least one heteroatom. Heteroatoms include, but are not limited to, O, S, Se, N, P, B, Si, Ge, and Se. In many cases, O, S, N, or B are preferred heteroatoms. Monocyclic heteroaromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the rings may have one to six heteroatoms. Polycyclic heterocyclic systems may have two or more aromatic rings, wherein two atoms are common to two adjacent rings (the rings are "fused"), and at least one of the rings is a heteroaryl. Polycyclic heteroaromatic ring systems may have one to six heteroatoms in each ring. Preferred heteroaryls are those containing three to thirty carbon atoms, preferably three to twenty-four carbon atoms, three to eighteen carbon atoms, and more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenene, furan, thiophene, benzofuran, benzothiophene, benzoselenene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, Indazole, indoxazine, benzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, cinnamoline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, selenophenodipyridine, aziborane, cycloborane, 5λ 2 ,9λ 2 -diaza-13b-boronanaphene[2,3,4-de]anthracene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazolium and 5,9-dioxa-13b-boronazona[3,2,1-de]anthracene; preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazolium, pyridine, triazine, benzimidazole, 5λ 2 ,9λ 2 -diaza-13b-boronanaphene[2,3,4-de]anthracene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazo[3,2-a]imidazo[3,2,1-de]anthracene. Additionally, heteroaryl groups can be further substituted or fused.

[0061] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, benzimidazole, and 5λ are included. 2 ,9λ 2-diaza-13b-boronanaphene[2,3,4-de]anthracene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazo, 5,9-dioxa-13b-boronazona[3,2,1-de]anthracene groups, and their corresponding aza analogs are of particular interest.

[0062] In many cases, the general substituents are selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boranalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenyl, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0063] In some cases, preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, boroalkyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof.

[0064] In some cases, more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, germanyl, boronyl, aryl, heteroaryl, nitrile, thio, and combinations thereof.

[0065] In some cases, even more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitriles and combinations thereof.

[0066] In other cases, the most preferred general substituent is selected from the group consisting of: deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0067] The terms "substituted" and "substituted" refer to substituents other than H being bonded to the relevant position, such as carbon or nitrogen. For example, when R... 1 When representing a single substitution, then an R 1 It must not be H (i.e., substitution). Similarly, when R 1 When representing disubstituted substitution, then the two Rs 1 It must not be H. Similarly, when R... 1 When R represents zero or no substitution, 1 For example, it could be hydrogen atoms with all available valences in the ring atom, such as carbon atoms in benzene and nitrogen atoms in pyrrole, or simply none for ring atoms with fully saturated valences, such as nitrogen atoms in pyridine. The maximum possible number of substitutions in a ring structure will depend on the total number of available valences in the ring atoms.

[0068] As used herein, “combination thereof” means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that can be conceived by one of ordinary skill in the art from the applicable list. For example, alkyl and deuterium can be combined to form partially or fully deuterated alkyl groups; halogen and alkyl groups can be combined to form haloalkyl substituents; and halogen, alkyl, and aryl groups can be combined to form haloaralkyl groups. In one instance, the term substitution includes a combination of two to four listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations containing up to forty atoms that are not hydrogen or deuterium, or combinations containing up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0069] The term "aza" in the phrases used herein, namely aza-dibenzofuran, aza-dibenzothiophene, etc., refers to the substitution of one or more CH groups in the corresponding aromatic ring by a nitrogen atom. For example, and without limitation, azatriphenylene covers dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derived compounds described above will be readily contemplated by those skilled in the art, and all such analogs are intended to be covered by the terminology set forth herein.

[0070] As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. US2011 / 0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further references to Ming Yan et al., Tetrahedron 2015, 71, 1425-30, and Atzrodt et al., Angewandte Chemie International Edition (Review) 2007, 46, 7744-65 (which are incorporated herein by reference in their entirety) describe efficient methods for the deuteration of methylene hydrogen in benzylamine and the replacement of aromatic cyclic hydrogens with deuterium, respectively.

[0071] As used herein, any specifically listed substituent, such as, but not limited to, methyl, phenyl, pyridyl, etc., includes its undeuterated, partially deuterated, and fully deuterated forms. Similarly, substituents, such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc., also include their undeuterated, partially deuterated, and fully deuterated forms. Unless otherwise specified, atoms in a chemical structure that are not completely filled with H or D should be considered to include their undeuterated, partially deuterated, and fully deuterated forms. For example, chemical structures This refers to C6H6, C6D6, C6H3D3, and any other partially deuterated variants thereof. Some common basic or fully deuterated groups include, but are not limited to, CD3, CD2C(CH3)3, C(CD3)3, and C6D5.

[0072] It should be understood that when a molecular fragment is described as a substituent or additionally linked to another part, its name can be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or linked fragments are considered equivalent.

[0073] In some cases, a pair of substituents in a molecule may optionally be joined or fused to form a ring. Preferred rings are five- to nine-membered carbon rings or heterocycles, including both cases where the ring formed by the pair of substituents is partially saturated and cases where the ring formed by the pair of substituents is partially unsaturated. In other cases, a pair of adjacent substituents may optionally be joined or fused to form a ring. As used herein, “adjacent” means that the two substituents involved may be adjacent to each other on the same ring, or on two neighboring rings having two closest available substituted positions (such as the 2, 2' positions in biphenyl or the 1, 8 positions in naphthalene).

[0074] B. Compounds disclosed herein

[0075] In one aspect, this disclosure provides a formula Ir(L) A ) x (L B ) y Compounds containing formula I The structure, wherein:

[0076] Each of x and y is independently 1 or 2, and x + y = 3;

[0077] X 1 To X 17 Each of them is independently C or N;

[0078] R A R B R CR D and R E Each of these terms independently represents a single substitution up to the maximum permissible substitution or no substitution;

[0079] Each R 1 R 2 R 3 R 4 R A R B R C R D and R E Substituents that are independently hydrogen or selected from the group of universal substituents as defined herein;

[0080] Any two substituents can join or fuse to form a ring;

[0081] R 1 R 2 R 3 Or R 4 At least one of them is not hydrogen, deuterium, or halogen;

[0082] R 1 R 2 R 3 and R 4 Each of them has a corresponding cone angle R. 1 (CA), R 2 (CA), R 3 (CA) and R 4 (CA);

[0083] R 1 R 2 R 3 and R 4 Each of them has a corresponding van der Waals surface area R. 1 (VdW), R 2 (VdW), R 3 (VdW) and R 4 (VdW); and

[0084] At least one of the following is true:

[0085] (i) And R 1 (CA) or R 3 At least one of (CA) is greater than or equal to the target cone angle.

[0086] (ii) And R 1 (CA) or R 4 At least one of (CA) is greater than or equal to the target cone angle.

[0087] (iii) And R 2 (CA) or R 3 At least one of (CA) is greater than or equal to the target cone angle, or

[0088] (iv) And R 2 (CA) or R 4 At least one of (CA) is greater than or equal to the target cone angle;

[0089] The target cone angle is 35 degrees.

[0090] As used herein, the “cone angle” is defined by points A, B, and C, where A is the carbon atom of the ring directly bonded to B, and B is the substituent directly bonded to A (e.g., the α-position) (e.g., R). 1 R 2 R 3 Or R 4 The atoms on the molecule are C, and C is a non-hydrogen atom of the substituent that produces the maximum cone angle (BAC). The cone angle is calculated using the configuration of the molecule with the lowest energy, which is determined by density functional theory (DFT) calculations using the B3LYP functional and the LACVP* basis set. 1 Examples of 1,2-dimethylpropyl are shown below:

[0091] For applicable substituents (R) 1 To R 4 In cases where a substituent, A, is bonded to or fused with another atom Y on the ring, a morphological distance map of the substituent is generated for each fused atom (e.g., A and Y) to determine which atom of the applicable substituent should be used to measure the cone angle. The morphological distance map measures the distance from an atom (A or Y) to another atom (which can be considered part of the applicable substituent) as the shortest distance according to the number of bonds. An example of the morphological distance map for A is used in the following instance, where R... 1 With bond to X 13 R A Condensation: The corresponding topographic distances of Y with the same structure are shown in the following structures: Only atoms whose morphological distance to atom A is shorter than or equal to their morphological distance to atom Y are considered for cone angle calculation. Therefore, in this example, the cone angle is then defined as:

[0092] As used in this paper, the “van der Waals surface area” of the substituents was determined using the computational chemistry suite Maestro. The geometry used was determined by the substituents of interest (e.g., R0). 1 To R 4The lowest energy structure of the substituted benzene ring is determined by DFT using the B3LYP functional and 6-31G*. The benzene ring is then removed, and only atoms on the substituents are considered for van der Waals surface area calculations.

[0093] In some embodiments, the formula Ir(L) A ) x (L B ) y It is basically composed of Equation I. In some embodiments, Equation Ir(L A ) x (L B ) y It has the structure of Formula I.

[0094] In some embodiments of Formula I, at least one R 1 R 2 R 3 R 4 R A R B R C R D Or R E Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R 1 Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R 2 Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R 3 Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R 4 Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R A Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R B Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R C Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R D Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R E Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R 1 R 2 R 3 R 4 R A R B R C R D Or RE The group consisting of preferred general substituents as defined herein is selected.

[0095] In some embodiments of Formula I, at least one R 1 R 2 R 3 R 4 R A R B R C R D and R E It is partially or fully deuterated. In some embodiments, at least one R A It is partially or fully deuterated. In some embodiments, at least one R B It is partially or fully deuterated. In some embodiments, at least one R C It is partially or fully deuterated. In some embodiments, at least one R D It is partially or fully deuterated. In some embodiments, at least one R E It is partially or fully deuterated. In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them is partially or completely deuterated.

[0096] In some embodiments, the target cone angle is 50 degrees. In some embodiments, the target cone angle is 60 degrees. In some embodiments, the target cone angle is 70 degrees. In some embodiments, the target cone angle is 80 degrees. In some embodiments, the target cone angle is 90 degrees. In some embodiments, the target cone angle is 100 degrees. In some embodiments, the target cone angle is 110 degrees. In some embodiments, the target cone angle is 120 degrees. In some embodiments, the target cone angle can be up to 180 degrees.

[0097] In some embodiments, or or

[0098] In some embodiments, or or

[0099] In some embodiments, or or

[0100] In some embodiments, or or

[0101] In some embodiments, or or or

[0102] In some embodiments, or or or

[0103] In some embodiments, or or or

[0104] In some embodiments, or or or

[0105] In some embodiments, R 1 (VdW)+R 3 (VdW) in 1000 to or 800 to or 600 to Or 400 to Within the range.

[0106] In some embodiments, R 1 (VdW)+R 4 (VdW) in 1000 to or 800 to or 600 to Or 400 to Within the range.

[0107] In some embodiments, R 2 (VdW)+R 3 (VdW) in 1000 to or 800 to or 600 to Or 400 to Within the range.

[0108] In some embodiments, R 2 (VdW)+R 4 (VdW) in 1000 to or 800 to or 600 to Or 400 to Within the range.

[0109] In some embodiments, R 1 R 2 R 3 R 4 R A R B R C R D and R E Each of these is independently hydrogen or a substituent selected from the group of preferred general substituents as defined herein. In some embodiments, R 1 R 2 R 3 R 4 R A R B R C R D and R E Each of these is independently hydrogen or a substituent selected from the group of more preferred general substituents as defined herein. In some embodiments, R 1 R 2 R 3 R 4 R A R B R C R D and R E Each of these is independently hydrogen or a substituent selected from the group consisting of even more preferred general substituents as defined herein. In some embodiments, R 1 R 2 R 3 R 4 R A R B R C R D and R E Each of them is independently hydrogen or a substituent selected from the group of the most preferred general substituents as defined herein.

[0110] 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 )2.

[0111] In some embodiments, X 1 To X 4 Each of them is C. In some embodiments, X 1 To X 4At least one of them is N. In some embodiments, X 1 To X 4 One of them is N.

[0112] In some embodiments, X 5 To X 8 Each of them is C. In some embodiments, X 5 To X 8 At least one of them is N. In some embodiments, X 5 To X 8 One of them is N.

[0113] In some embodiments, X 9 To X 11 Each of them is C. In some embodiments, X 9 To X 11 At least one of them is N. In some embodiments, X 9 To X 11 One of them is N.

[0114] In some embodiments, X 12 To X 14 Each of them is C. In some embodiments, X 12 To X 14 At least one of them is N. In some embodiments, X 12 To X 14 One of them is N.

[0115] In some embodiments, X 14 It is N.

[0116] In some embodiments, X 15 To X 17 Each of them is C. In some embodiments, X 15 To X 17 At least one of them is N. In some embodiments, X 15 To X 17 One of them is N.

[0117] In some embodiments, X 1 To X 17 Each of them is C.

[0118] In some embodiments, And R 1 (CA) or R 3 At least one of (CA) is greater than or equal to the target cone angle.

[0119] In some embodiments, And R 1 (CA) or R4 At least one of (CA) is greater than or equal to the target cone angle.

[0120] In some embodiments, And R 2 (CA) or R 3 At least one of (CA) is greater than or equal to the target cone angle.

[0121] In some embodiments, And R 2 (CA) or R 4 At least one of (CA) is greater than or equal to the target cone angle.

[0122] In some embodiments, at least two of conditions (i) to (iv) are true. In some embodiments, at least three of conditions (i) to (iv) are true. In some embodiments, each of conditions (i) to (iv) is true.

[0123] In some embodiments, the compound comprises the structure of formula II.

[0124] in:

[0125] X 18 To X 21 Each of them is independently C or N;

[0126] Y 1 Select from the following groups: 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', and GeRR';

[0127] R D' Indicates single substitution up to the maximum permissible substitution or no substitution;

[0128] Each R D' R and R' are independently hydrogen or substituents selected from the group of universal substituents as defined herein; and

[0129] Any two substituents can join or fuse to form a ring.

[0130] In some embodiments of Formula II, at least one R 1 R 2 R 3 R 4 R A R B R C R D' Or R ESelected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R 1 Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R 2 Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R 3 Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R 4 Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R A Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R B Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R C Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R D' Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R E Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R 1 R 2 R 3 R 4 R A R B R C R D' Or R E The group consisting of preferred general substituents as defined herein is selected.

[0131] In some embodiments of Formula II, at least one R 1 R 2 R 3 R 4 R A R B R C R D' and R E It is partially or fully deuterated. In some embodiments, at least one R A It is partially or fully deuterated. In some embodiments, at least one R B It is partially or fully deuterated. In some embodiments, at least one R C It is partially or fully deuterated. In some embodiments, at least one R D' It is partially or fully deuterated. In some embodiments, at least one R E It is partially or fully deuterated. In some embodiments, R 1 R2 R 3 Or R 4 At least one of them is partially or completely deuterated.

[0132] In some embodiments, X 18 To X 21 Each of them is C. In some embodiments, X 18 To X 21 At least one of them is N. In some embodiments, X 18 To X 21 One of them is N. In some embodiments, X 18 It is N. In some embodiments, X 19 It is N. In some embodiments, X 20 It is N. In some embodiments, X 21 It is N.

[0133] In some embodiments, Y 1 Bond to X 5 .

[0134] In some embodiments, Y 1 Bond to X 6 In some such embodiments, with Y 1 The opposite dashed bond to X 5 In other embodiments, with Y 1 The opposite dashed bond to X 7 .

[0135] In some embodiments, Y 1 Bond to X 7 In some such embodiments, with Y 1 The opposite dashed bond to X 6 In other embodiments, with Y 1 The opposite dashed bond to X 8 .

[0136] In some embodiments, Y 1 Bond to X 8 .

[0137] In some embodiments, Y 1 Choose from the group consisting of O, S, and Se. In some embodiments, Y 1 It is O. In some embodiments, Y 1 Select from the group consisting of BR, NR, and PR. In some embodiments, Y 1 The group consisting of BRR', CRR', SiRR', and GeRR' is selected. In some embodiments, Y 1The group consisting of P(O)R, C=O, C=S, C=Se, C=NR, C=CRR', S=O, and SO2 is selected. In some embodiments, Y 1 It is CRR'.

[0138] In some embodiments of Formula I or Formula II, when R 1 When it is an alkyl group, it contains at least 5, 6, or 7 carbon atoms. In some embodiments of Formula I or Formula II, when R 2 When it is an alkyl group, it contains at least 5, 6, or 7 carbon atoms. In some embodiments of Formula I or Formula II, when R 1 and R 2 When all are alkyl groups, they collectively contain at least 5, 6, or 7 carbon atoms. In some embodiments of Formula I or II, when R... 1 and R 2 When all are alkyl groups, each contains at least 5, 6, or 7 carbon atoms. In some embodiments of Formula I or Formula II, when R 1 Or R 2 When it is silyl or germanyl, the silyl or germanyl group contains at least four or more carbon atoms. In some embodiments of Formula I or Formula II, R 1 Not -SiMe 3 or GeMe 3 In some embodiments of Formula I or Formula II, R 1 It is not silyl or germanyl. In some embodiments of Formula I or II, R 1 It is not a silyl or germanyl group containing 3 or fewer carbon atoms.

[0139] In some embodiments of Formula I or Formula II, R 3 It is an alkyl, silyl, or germanyl group. In some such embodiments, the alkyl group contains at least four or more carbon atoms. In some embodiments of Formula I or II, R 4 It is an alkyl, silyl, or germanyl group. In some such embodiments, the alkyl group contains at least four or more carbon atoms. In some embodiments, R 3 and R 4 Each of them is an alkyl, silyl, or germanyl group. In some such embodiments, the alkyl group contains at least four or more carbon atoms.

[0140] 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 equal to or greater than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1.

[0141] In some embodiments, the first ligand L A Electron-withdrawing groups comprising structures selected from the following EWG1 list: F, CF3, CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC. + N(R k2 )3、(R k2 )2CCN、(R k2 )2CCF3、CNC(CF3)2、BR k3 R k2 Substituted or unsubstituted dibenzoboranecyclopentadiene, 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, ketones, carboxylic acids, esters, nitriles, isonitriles, sulfinyl groups, sulfonyl groups, partially and fully fluorinated alkyl groups, partially and fully fluorinated aryl groups, partially and fully fluorinated heteroaryl groups, cyano-containing alkyl groups, cyano-containing aryl groups, cyano-containing heteroaryl groups, isocyanates,

[0142]

[0143]

[0144] Each R k1 Indicates single substitution up to the maximum permissible substitution or no substitution;

[0145] Where Y G Choose from the following groups: BR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f SiR e R f and GeR e R f' ;and

[0146] Where R k1 R k2 R k3R e and R f Each of them is independently hydrogen or a substituent selected from the group of universal substituents defined herein.

[0147] In some embodiments, the first ligand L A Includes electron-withdrawing groups from the group consisting of structures selected from the following EWG2 list:

[0148]

[0149]

[0150]

[0151] In some embodiments, the first ligand L A Includes electron-withdrawing groups from the group consisting of structures selected from the following EWG3 list:

[0152]

[0153] In some embodiments, the first ligand L A Includes electron-withdrawing groups from the group consisting of structures selected from the following EWG4 list:

[0154] In some embodiments, the first ligand L A Electron-withdrawing groups that are π-electron deficient and comprise structures selected from the following Pi-EWG lists: 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 k3Substituted or unsubstituted dibenzoborane heterocyclopentadiene, 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, sulfinyl groups, sulfonyl groups, partially and fully fluorinated aryl groups, partially and fully fluorinated heteroaryl groups, cyano-containing aryl groups, cyano-containing heteroaryl groups, isocyanates,

[0155] The variables are the same as those previously defined.

[0156] In some embodiments, the compound comprises an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the Pi-EWG list as defined herein.

[0157] In some embodiments, L B Includes electron-withdrawing groups from the EWG1 list as defined herein. In some embodiments, L B Includes electron-withdrawing groups from the EWG2 list as defined herein. In some embodiments, L B Includes electron-withdrawing groups from the EWG3 list as defined herein. In some embodiments, L B Includes electron-withdrawing groups from the EWG4 list as defined herein. In some embodiments, L B Includes electron-withdrawing groups from the Pi-EWG list as defined herein.

[0158] In some embodiments, at least one R A It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R A It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R A It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R AIt is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R A It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0159] In some embodiments, at least one R B It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R B It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R B It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R B It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R B It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

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

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

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

[0163] In some embodiments, R 1 It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, R 1 It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, R 1 It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, R 1 It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, R 1 It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0164] In some embodiments, R 2 It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, R 2 It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, R 2 It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, R 2 It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, R 2 It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0165] In some embodiments, R 3 It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, R 3 It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, R 3 It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, R 3 It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, R 3It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0166] In some embodiments, R 4 It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, R 4 It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, R 4 It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, R 4 It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, R 4 It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0167] In some embodiments of Formula II, at least one R D' It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R D' It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R D' It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R D' It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R D' It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0168] In some embodiments of Formula II, at least one R or R' is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R or R' is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R or R' is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R or R' is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R or R' is or contains an electron-withdrawing group from the Pi-EWG list as defined herein.

[0169] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them contains a tertiary alkyl group. In some embodiments, R 1 R 2 R 3 Or R 4At least two of them independently contain tertiary alkyl groups. In some embodiments, R 1 R 2 R 3 Or R 4 At least three of them independently contain tertiary alkyl groups.

[0170] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them contains a tertiary alkyl group, and the remaining R 1 R 2 R 3 Or R 4 At least two of them independently contain secondary alkyl groups.

[0171] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them contains a tertiary alkyl group, and the remaining R 1 R 2 R 3 Or R 4 At least one of them contains an aryl group.

[0172] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them contains a tertiary alkyl group, and the remaining R 1 R 2 R 3 Or R 4 At least two of them independently contain aryl groups.

[0173] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them contains five or more carbon atoms. In some embodiments, R 1 R 2 R 3 Or R 4 At least two of them independently contain five or more carbon atoms. In some embodiments, R 1 Or R 2 At least one of them contains five or more carbon atoms. In some embodiments, R 3 Or R 4 At least one of them contains five or more carbon atoms.

[0174] In some embodiments, R 1R 2 R 3 Or R 4 At least one of them contains six or more carbon atoms. In some embodiments, R 1 R 2 R 3 Or R 4 At least two of them independently contain six or more carbon atoms. In some embodiments, R 1 Or R 2 At least one of them contains six or more carbon atoms. In some embodiments, R 3 Or R 4 At least one of them contains 6 or more carbon atoms.

[0175] In some embodiments, R 1 Or R 2 At least one of them contains a tertiary alkyl group.

[0176] In some embodiments, R 1 Or R 2 At least one of them contains a tertiary alkyl group, said tertiary alkyl group comprising at least one cyclic moiety. In some such embodiments, at least one cyclic moiety is a cycloalkyl group.

[0177] In some embodiments, R 1 Or R 2 At least one of the components comprises a tertiary alkyl group, said tertiary alkyl group comprising at least two cyclic moieties. In some such embodiments, the two cyclic moieties are bonded by a single bond or a spiro atom, while in other embodiments, the two cyclic moieties may be fused.

[0178] In some embodiments, R 1 Or R 2 At least one of them contains an adamantyl group.

[0179] In some embodiments, R 1 R 2 R 3 and R 4 The combination contains a total of at least 10 carbon atoms. In some embodiments, R 1 R 2 R 3 and R 4 The combination contains a total of at least 11 carbon atoms. In some embodiments, R 1 R 2 R 3 and R 4 The combination contains a total of at least 12 carbon atoms. For clarity, although the Ir complex will include a total of 3 ligands (two L... A And an L B , or an LA and two L B However, this limitation refers to an L. A And an L B R 1 To R 4 The total number of carbon atoms in it.

[0180] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them contains a polycyclic nonaromatic ring system.

[0181] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them comprises a polycyclic non-aromatic ring system having at least one single-atom bridge. In some such embodiments, the single-atom bridge may be a methylene (CH2) bridge.

[0182] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them comprises a polycyclic nonaromatic ring system having at least two single-atom bridges. In some such embodiments, any one or both single-atom bridges may be methylene (CH2) bridges.

[0183] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them comprises a polycyclic nonaromatic ring system having at least one diatomic bridge. In some such embodiments, the diatomic bridge may be an ethylene (C2H4) bridge.

[0184] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them comprises a polycyclic nonaromatic ring system having at least two diatomic bridges. In some such embodiments, any one or both diatomic bridges may be ethylene (C2H4) bridges.

[0185] In some embodiments, R 1 R 2 R 3 and R 4 At least one of them is a multi-ring spiral system.

[0186] In some embodiments, R 1 R 2 R3 Or R 4 At least one of them contains a silane or germanyl group comprising at least four carbon atoms. In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them contains a silyl or germanyl group comprising at least 5 carbon atoms.

[0187] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them comprises a silyl or germanyl group including at least one cyclic moiety. In some such embodiments, at least one cyclic group may be a cycloalkyl group. In some such embodiments, at least one cyclic group may be an aryl or heteroaryl group.

[0188] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them comprises a silyl or germanyl group comprising at least two cyclic moieties. In some embodiments, each of the at least two cyclic moieties may be independently cycloalkyl, aryl, or heteroaryl. In some embodiments, at least one of the two cyclic moieties is cycloalkyl. In some embodiments, at least one of the two cyclic moieties is aryl or heteroaryl.

[0189] In some embodiments, R 1 R 2 R 3 and R 4 At least two of the moieties contain portions selected from the group consisting of: tertiary alkyl, polycyclic nonaromatic ring systems, silyl groups containing at least 4 carbon atoms, germanyl groups containing at least 4 carbon atoms, and moieties containing at least 5 carbon atoms.

[0190] In some embodiments, R 1 R 2 R 3 and R 4 At least three of the moieties in the formula contain portions selected from the group consisting of: tertiary alkyl, polycyclic nonaromatic ring systems, silyl groups containing at least 4 carbon atoms, germanyl groups containing at least 4 carbon atoms, and moieties containing at least 5 carbon atoms.

[0191] In some embodiments, R 1 and R 2 Same. In some embodiments, R 1 and R 2 different.

[0192] In some embodiments, R 3 and R 4 Same. In some embodiments, R 3 and R 4 different.

[0193] In some embodiments, R 1 R 2 R 3 Or R 4 At least one of them is selected from the group consisting of the structures in Listing 1 below:

[0194]

[0195]

[0196] In some embodiments, R 1 R 2 R 3 Or R 4 At least two of them are independently selected from the group consisting of the structures in Listing 1 as defined herein. In some embodiments, R 1 R 2 R 3 Or R 4 At least three of them are independently selected from the groups consisting of the structures in Listing 1 as defined herein. In some embodiments, R 1 R 2 R 3 and R 4 Each of the structures in the list is independently selected from the group of structures defined in List 1 of this document.

[0197] In some embodiments, at least one R A Not hydrogen. In some embodiments, each R A It is hydrogen.

[0198] In some embodiments, at least one R A It contains at least one C atom. In some embodiments, at least one R... A It contains at least two C atoms. In some embodiments, at least one R... A It contains at least three C atoms. In some embodiments, at least one R... A It contains at least four carbon atoms.

[0199] In some embodiments, at least one R A It includes substituents selected from the group consisting of: alkyl, cycloalkyl, silalkyl, germanalkyl, aryl, heteroaryl, and combinations thereof.

[0200] In some embodiments, two RA Joined or fused to form a cyclic portion A1, wherein portion A1 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbon ring or heterocyclic ring.

[0201] In some embodiments, portion A1 is selected from the group consisting of the following list of cyclic portions: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole-derived carbenes, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzene The following are included: thiazole, benzo[a]selenide, aza-benzo[a]selenide, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole-derived carbenes, aza-benzimidazole-derived carbenes, 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, part A1 is benzene.

[0202] In some embodiments, at least one R B Not hydrogen. In some embodiments, each R B It is hydrogen.

[0203] In some embodiments, at least one R B It contains at least one C atom. In some embodiments, at least one R... B It contains at least two C atoms. In some embodiments, at least one R... B It contains at least three C atoms. In some embodiments, at least one R... B It contains at least four carbon atoms.

[0204] In some embodiments, at least one R B It includes substituents selected from the group consisting of: alkyl, cycloalkyl, silalkyl, germanalkyl, aryl, heteroaryl, and combinations thereof.

[0205] In some embodiments, two R B Joined or fused to form a cyclic portion B1, wherein portion B1 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbon ring or heterocyclic ring.

[0206] In some embodiments, portion B1 is selected from the group consisting of the list of cyclic portions as defined herein. In some embodiments, portion B1 is a benzofuran. In some embodiments, portion B1 is a benzofuran, wherein the furan is related to X. 15 and X 16 Condensation.

[0207] In some embodiments, at least one R C Not hydrogen. In some embodiments, each R C It is hydrogen.

[0208] In some embodiments, at least one R C It contains at least one C atom. In some embodiments, at least one R... C It contains at least two C atoms. In some embodiments, at least one R... C It contains at least three C atoms. In some embodiments, at least one R... C It contains at least four carbon atoms.

[0209] In some embodiments, at least one R C It includes substituents selected from the group consisting of: alkyl, cycloalkyl, silalkyl, germanalkyl, aryl, heteroaryl, and combinations thereof.

[0210] In some embodiments, two R C Joined or fused to form a cyclic portion C1, wherein portion C1 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbon ring or heterocyclic ring.

[0211] In some embodiments, portion C1 is selected from the group consisting of the list of cyclic portions as defined herein. In some embodiments, portion C1 is benzene. In some embodiments, portion C1 is pyridine. In some embodiments, portion C1 is a 5-membered ring. In some embodiments, portion C1 is a 6-membered ring.

[0212] In some embodiments, at least one R D Not hydrogen. In some embodiments, each R D It is hydrogen.

[0213] In some embodiments, at least one R D It contains at least one C atom. In some embodiments, at least one R... D It contains at least two C atoms. In some embodiments, at least one R... D It contains at least three C atoms. In some embodiments, at least one R... D It contains at least four carbon atoms.

[0214] In some embodiments, at least one R D It includes substituents selected from the group consisting of: alkyl, cycloalkyl, silalkyl, germanalkyl, aryl, heteroaryl, and combinations thereof.

[0215] In some embodiments, two R DJoined or fused to form a cyclic portion D1, wherein portion D1 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbon ring or heterocyclic ring.

[0216] In some embodiments, portion D1 is selected from the group consisting of the list of cyclic portions as defined herein. In some embodiments, portion D1 is a benzofuran. In some embodiments, portion D1 is a benzofuran, wherein the furan ring contains X. 5 To X 8 Ring fusion.

[0217] In some embodiments, part D' is a ring D (containing X) 5 To X 8 A combination of a ring (D1) and a portion D1, wherein portion D' comprises portion D1' (which includes ring D) and portion D1" (which is fused with portion D1'), wherein each of portions D1' and D1" is independently a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbon ring or heterocyclic ring. In some embodiments, each of portions D1' and D1" is independently selected from the group consisting of a list of cyclic portions as defined herein. In some embodiments, portion D1' is a benzofuran, wherein the furan is fused with a ring containing X 5 To X 8 The ring is fused, and part of D1" is benzene or naphthalene.

[0218] In some embodiments of Formula II, at least one R D' It is not hydrogen. In some embodiments of Formula II, each R D' It is hydrogen.

[0219] In some embodiments of Formula II, at least one R D' It contains at least one C atom. In some embodiments of Formula II, at least one R... D' It contains at least two C atoms. In some embodiments of Formula II, at least one R... D' It contains at least three C atoms. In some embodiments of Formula II, at least one R... D' It contains at least four carbon atoms.

[0220] In some embodiments of Formula II, at least one R D' It includes substituents selected from the group consisting of: alkyl, cycloalkyl, silalkyl, germanalkyl, aryl, heteroaryl, and combinations thereof.

[0221] In some embodiments of Formula II, the two R D'Joined or fused to form a cyclic portion D2, wherein portion D2 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbon ring or heterocyclic ring.

[0222] In some embodiments of Formula II, portion D2 is selected from the group consisting of the list of cyclic portions as defined herein. In some embodiments of Formula II, portion D2 is a benzofuran. In some embodiments of Formula II, portion D2 is a benzofuran, wherein the furan contains X 5 To X 8 The ring fusion. In some embodiments of Formula II, part of D2 is benzofuran, wherein the furan is fused with X. 18 To X 21 Ring fusion.

[0223] In some embodiments of Formula II, part of D2 is benzene or naphthalene.

[0224] In some embodiments, at least one R E Not hydrogen. In some embodiments, each R E It is hydrogen.

[0225] In some embodiments, at least one R E It contains at least one C atom. In some embodiments, at least one R... E It contains at least two C atoms. In some embodiments, at least one R... E It contains at least three C atoms. In some embodiments, at least one R... E It contains at least four carbon atoms.

[0226] In some embodiments, at least one R E It includes substituents selected from the group consisting of alkyl, cycloalkyl, silalkyl, germanalkyl, aryl, heteroaryl, and combinations thereof. In some embodiments, at least one R E It is an aryl group.

[0227] In some embodiments, X 10 R at the location E It includes substituents selected from the group consisting of: alkyl, cycloalkyl, silalkyl, germanalkyl, aryl, heteroaryl, and combinations thereof. In some embodiments, X 10 R at the location E It is an aryl group.

[0228] In some embodiments, at least one R E The group consisting of the structures defined in Listing 1 herein. In some embodiments, X 10 R at the location E Select the group consisting of the structures in List 1 as defined in this article.

[0229] In some embodiments, ligand L A Select the group consisting of the structures in List 2 below:

[0230]

[0231]

[0232] in:

[0233] X1 to X 23 Each of them is independently C or N;

[0234] Each of Y1 and Y2 is independently selected from the following groups: 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', and GeRR';

[0235] R D1 and R D2 Each of these terms independently represents a single substitution up to the maximum permissible substitution or no substitution;

[0236] Each R, R', R D1 and R D2 Independently, it is hydrogen or a substituent selected from the group of universal substituents as defined herein; and

[0237] Any two substituents can join or fuse to form a ring.

[0238] In ligand L A Selected from some embodiments in Listing 2, containing R E R 3 and R 4 The rings can be selected from groups consisting of the following structures (List A1):

[0239]

[0240]

[0241]

[0242]

[0243]

[0244] The dotted line connects to the N in the imidazole ring.

[0245] In ligand L A In some embodiments selected from Listing 2, at least one R C R D R D1 R D2 Or R E Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R C Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R D Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R D1 Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R D2 Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R E Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R C R D R D1 R D2 Or R E The group consisting of preferred general substituents as defined herein is selected.

[0246] In ligand L A Selected from some embodiments in Listing 2, R C R D R D1 R D2 Or R E At least one of them is partially or fully deuterated. In some embodiments, at least one R C It is partially or fully deuterated. In some embodiments, at least one R E It is partially or fully deuterated. In some embodiments, at least one R D It is partially or fully deuterated. In some embodiments, at least one R D1 It is partially or fully deuterated. In some embodiments, at least one R D2 It is partially or completely deuterated.

[0247] In ligand L A In some embodiments selected from Listing 2, at least one R C It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R C It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R CIt is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R C It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R C It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0248] In ligand L A In some embodiments selected from Listing 2, at least one R D It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R D It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R D It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R D It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R D It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0249] In ligand L A In some embodiments selected from Listing 2, at least one R D1 It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R D1 It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R D1 It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R D1 It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R D1 It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0250] In ligand L A In some embodiments selected from Listing 2, at least one R D2 It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R D2 It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R D2 It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R D2It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R D2 It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0251] In ligand L A In some embodiments selected from Listing 2, at least one R E It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R E It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R E It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R E It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R E It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0252] In some embodiments, ligand L A Select the group consisting of the structures defined in Listing 3 below:

[0253]

[0254]

[0255] in:

[0256] Y A and Y B Each of them is independently selected from the following groups: 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', and GeRR';

[0257] R CC R DD R DD1 R DD2 and R EE Each of these terms independently represents a single substitution up to the maximum permissible substitution or no substitution;

[0258] Each R, R', R CC R DD R DD1 R DD2 and R EE Substituents that are independently hydrogen or selected from the group of universal substituents as defined herein;

[0259] The remaining variables are the same as previously defined; and

[0260] Any two substituents can join or fuse to form a ring.

[0261] In ligand L A In some embodiments selected from Listing 3, R is included EE R 3 and R 4 The rings can be selected from groups of structures as defined in List A1 of this document.

[0262] In ligand L A In some embodiments selected from Listing 3, at least one R CC R DD R DD1 R DD2 Or R EE Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R CC Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R DD Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R DD1 Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R DD2 Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R EE Selected from the group consisting of universal substituents as defined herein. In some embodiments, at least one R CC R DD R DD1 R DD2 Or R EE The group consisting of preferred general substituents as defined herein is selected.

[0263] In ligand L A Selected from some embodiments in Listing 3, R CC R DD R DD1 R DD2 Or R EE At least one of them is partially or fully deuterated. In some embodiments, at least one R CC It is partially or fully deuterated. In some embodiments, at least one R DD It is partially or fully deuterated. In some embodiments, at least one R DD1 It is partially or fully deuterated. In some embodiments, at least one R DD2 It is partially or fully deuterated. In some embodiments, at least one R EEIt is partially or completely deuterated.

[0264] In ligand L A In some embodiments selected from Listing 3, at least one R CC It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R CC It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R CC It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R CC It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R CC It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0265] In ligand L A In some embodiments selected from Listing 3, at least one R DD It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R DD It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R DD It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R DD It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R DD It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0266] In ligand L A In some embodiments selected from Listing 3, at least one R DD1 It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R DD1 It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R DD1 It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R DD1 It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R DD1 It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0267] In ligand L A In some embodiments selected from Listing 3, at least one R DD2It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R DD2 It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R DD2 It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R DD2 It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R DD2 It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0268] In ligand L A In some embodiments selected from Listing 3, at least one R EE It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R EE It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R EE It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R EE It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R EE It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0269] In some embodiments, ligand L A Selected from L Ai (Rm)(Rn)(Ro)(Rp)(Rq)(Rr), where i is an integer from 1 to 38, Rm is selected from R131 to R250, Rn is selected from R1 to R250, each of Ro, Rp, Rq and Rr is independently selected from R1 to R130, and L A1 (R131)(R1)(R1)(R1)(R1)(R1) to L A38 Each definition in (R250)(R250)(R130)(R130)(R130)(R130) is defined in the following Listing 4:

[0270]

[0271]

[0272]

[0273]

[0274] or the ligand L described thereinA Selected from L A'i' (Rm')(Rn)(Ro)(Rp)(Rq)(Rr), where i' is an integer from 1 to 38, Rm' is selected from R1 to R250, and L A'1 (R1)(R1)(R1)(R1)(R1)(R1) to L A'38 Each definition in (R250)(R250)(R130)(R130)(R130)(R130) is in the following Listing 5:

[0275]

[0276]

[0277]

[0278]

[0279] R1 to R130 have the structures defined in Listing 6 below:

[0280]

[0281] and

[0282] R131 to R250 have the structures defined in Listing 1 as defined herein.

[0283] In some embodiments, ligand L B Select the group consisting of the structures in List 7 below:

[0284] in:

[0285] R AA and R BB Each of these terms independently represents a single substitution up to the maximum permissible substitution or no substitution;

[0286] Each R AA and R BB Substituents that are independently hydrogen or selected from the group of universal substituents as defined herein;

[0287] The remaining variables are the same as previously defined; and

[0288] Any two substituents can join or fuse to form a ring.

[0289] In ligand L A Selected from some embodiments in Listing 7, RAA Or R BB At least one of them is partially or fully deuterated. In some embodiments, at least one R AA It is partially or fully deuterated. In some embodiments, at least one R BB It is partially or completely deuterated.

[0290] In ligand L A In some embodiments selected from Listing 7, at least one R AA It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R AA It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R AA It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R AA It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R AA It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0291] In ligand L A In some embodiments selected from Listing 7, at least one R BB It is or contains an electron-withdrawing group from the EWG1 list as defined herein. In some embodiments, at least one R BB It is or contains an electron-withdrawing group from the EWG2 list as defined herein. In some embodiments, at least one R BB It is or contains an electron-withdrawing group from the EWG3 list as defined herein. In some embodiments, at least one R BB It is or contains an electron-withdrawing group from the EWG4 list as defined herein. In some embodiments, at least one R BB It is or contains electron-withdrawing groups from the Pi-EWG list as defined herein.

[0292] In some embodiments, ligand L B Selected from L Bk , where k is an integer from 1 to 541, and L B1 To L B541 Each definition in the following Listing 8 is:

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306] In some embodiments, ligand L B Selected from L B'k' (Ri)(Rj)(Rk)(Rl), where k' is an integer from 1 to 35, where Ri is selected from the group consisting of R1 to R250, each of Rj, Rk, and Rl is independently selected from the group consisting of R1 to R250, and L B'k' Each of (Ri)(Rj)(Rk)(Rl) is defined in the following Listing 9:

[0307]

[0308]

[0309]

[0310] Where R1 to R130 have the structures defined in Listing 6 as defined herein; and

[0311] R131 to R250 have the structures defined in Listing 1 as defined herein.

[0312] In some embodiments, the first ligand L A Selected from L Ai (Rm)(Rn)(Ro)(Rp)(Rq)(Rr) or L A'i' (Rm')(Rn)(Ro)(Rp)(Rq)(Rr), where i is an integer from 1 to 38; i' is an integer from 1 to 38; and the ligand L BSelected from L Bk or L B'k' (Ri)(Rj)(Rk)(Rl), where k is an integer from 1 to 541, and k' is an integer from 1 to 35, where:

[0313] When the compound has the formula Ir(L) Ai (Rm)(Rn)(Ro)(Rp)(Rq)(Rr))(L Bk When )2, the compound is selected from Ir(L A1 (R131)(R1)(R1)(R1)(R1)(R1)(R1))(L B1 )2 to Ir(L A38 (R250)(R250)(R130)(R130)(R130)(R130))(L B541 Groups consisting of 2;

[0314] When the compound has the formula Ir(L) Ai (Rm)(Rn)(Ro)(Rp)(Rq)(Rr))(L B'k' When (Ri)(Rj)(Rk)(Rl))2, the compound is selected from Ir(L A1 (R131)(R1)(R1)(R1)(R1)(R1)(R1))(L B'1 (R131)(R1)(R1)(R1))2 to Ir(L A38 (R250)(R250)(R130)(R130)(R130)(R130))(L B'35 The group consisting of (R250)(R250)(R250)(R250))2;

[0315] When the compound has the formula Ir(L) A'i' (Rm')(Rn)(Ro)(Rp)(Rq)(Rr))(L B'k' When (Ri)(Rj)(Rk)(Rl))2, the compound is selected from Ir(L A1 (R1)(R1)(R1)(R1)(R1)(R1)(R1))(L B'1 (R131)(R1)(R1)(R1))2 to Ir(L A'38 (R250)(R250)(R130)(R130)(R130)(R130))(L B'35 The group consisting of (R250)(R250)(R250)(R250))2;

[0316] When the compound has the formula Ir(L) Ai (Rm)(Rn)(Ro)(Rp)(Rq)(Rr))2(LBk When the compound is selected from Ir(L) A1 (R131)(R1)(R1)(R1)(R1)(R1))2(L B1 ) to Ir(L A38 (R250)(R250)(R130)(R130)(R130)(R130))2(L B541 A group consisting of )

[0317] When the compound has the formula Ir(L) Ai (Rm)(Rn)(Ro)(Rp)(Rq)(Rr))2(L B'k' When (Ri)(Rj)(Rk)(Rl)), the compound is selected from Ir(L A1 (R131)(R1)(R1)(R1)(R1)(R1))2(L B'1 (R131)(R1)(R1)(R1)) to Ir(L A38 (R250)(R250)(R130)(R130)(R130)(R130))2(L B'35 The group consisting of (R250)(R250)(R250)(R250));

[0318] When the compound has the formula Ir(L) A'i' (Rm')(Rn)(Ro)(Rp)(Rq)(Rr))2(L B'k' When (Ri)(Rj)(Rk)(Rl)), the compound is selected from Ir(L A1 (R1)(R1)(R1)(R1)(R1)(R1)(R1))2(L B'1 (R131)(R1)(R1)(R1)) to Ir(L A'38 (R250)(R250)(R130)(R130)(R130)(R130))2(L B'35 The group consists of (R250)(R250)(R250)(R250)).

[0319] In some embodiments, the compound is selected from the group consisting of the structures in List 10 below:

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327] In some embodiments, the formula Ir(L) described herein A ) x (L B ) y The compounds are partially or fully deuterated. In some embodiments, the formula Ir(L) described herein... A ) x (L B ) y The compounds are fully deuterated. In some embodiments, the formula Ir(L) described herein... A ) x (L B ) y The compound 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, the percentage of deuteration has its general meaning and includes the percentage of all possible hydrogen atoms (e.g., hydrogen or deuterium positions) occupied by deuterium atoms in the compound. In some embodiments, the carbon atoms constituting the ring coordinated to the metal M are fully or partially deuterated. In some embodiments, the carbon atoms contained in the polycyclic system coordinated to the metal M are fully or partially deuterated. In some embodiments, the substituents connected to the monocyclic or fused polycyclic system coordinated to the metal M are fully or partially deuterated.

[0328] In some embodiments, the Formula I compound emits at room temperature with a full width at half maximum (FWHM) equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. A narrower FWHM indicates better color purity for OLED display applications.

[0329] As defined above, Ir(L) A ) x (L B ) y In some embodiments of the heteroligand compound, ligand L A Having the first substituent R I The first substituent R I The first atom aI in ligand L A Of all the atoms, the one furthest from the metal M is ligand L. B (If present) having a second substituent R II The second substituent RII The first atom α-II in ligand L B Of all the atoms, it is the farthest from the metal M.

[0330] In such heterozygous compounds, vector V D1 and V D2 V can be defined as follows. D1 Let V represent the direction from metal M to the first atom aI, and let V be the vector. D1 The value of D 1 This indicates that metal M and the first substituent R I The straight-line distance between the first atoms aI in V. D2 This represents the direction from metal M to the first atom a-II, and the vector V D2 The value of D 2 This indicates that metal M and the second substituent R II The straight-line distance between the first atom a-II in the matrix.

[0331] In such heterocomplexes, a sphere with radius r is defined, the center of which is a metal M, and the radius r is such that the sphere encloses a non-substituent R in the compound. I and R II The minimum radius of all atoms in a portion; and where D 1 and D 2 At least one of them is at least larger than the radius r. In some embodiments, D 1 and D 2 At least one of them is at least 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6 or larger than the radius r. In some embodiments, D 1 and D 2 The two values ​​in the equation are at least 1.5, 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, or 17.6 greater than the radius r.

[0332] In some embodiments of such heteropolymer compounds, the compound has a transition dipole moment axis, and the transition dipole moment axis is related to the vector V. D1 and V D2 The angle between them is defined, where the transition dipole moment axis and the vector V are... D1 and V D2 The angle between them is less than 40°. In some embodiments, the transition dipole moment axis and the vector V are... D1 and V D2 The angle between them is less than 30°, 20°, 15° or 10°.

[0333] In some embodiments of such heteropolymer compounds, the compound has a vertical dipole ratio (VDR) of 0.33 or less. In some embodiments of such heteropolymer compounds, the compound has a VDR of 0.30, 0.25, 0.20, or 0.15 or less.

[0334] Those skilled in the art will readily understand the meaning of the terms "transition dipole moment axis" and "vertical dipole ratio" of a compound. However, the meanings of these terms can be found in U.S. Patent No. 10,672,997, the disclosure of which is incorporated herein by reference in its entirety. In U.S. Patent No. 10,672,997, the horizontal dipole ratio (HDR) of the compound is discussed, not the VDR. However, those skilled in the art will readily understand that VDR = 1 - HDR.

[0335] In some embodiments, the compound may be an emission dopant. In some embodiments, the compound may generate emission via phosphorescence, fluorescence, thermally activated delayed fluorescence, triplet-triplet annihilation, or a combination of these methods. In some embodiments, the emission dopant may be a racemic mixture or may be enriched with one enantiomer. In some embodiments, the compounds of the present invention may have different stereoisomers, such as fac and mer. The present compounds relate to individual isomers and mixtures of various isomers in any mixing ratio. In some embodiments, the compound may be homogeneous (each ligand is the same). In some embodiments, the compound may be mixed (at least one ligand is different from the others). In some embodiments, when more than one ligand coordinated to a metal is present, the ligands may all be the same. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, each ligand may be different from all the other ligands. This also holds true in embodiments where a ligand coordinated to a metal may be linked to other ligands coordinated to the metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligand. Therefore, in the case where the ligands are linked together, in some embodiments all the ligands may be the same, and in some other embodiments at least one of the linked ligands may be different from the other ligands.

[0336] In another aspect of this disclosure, a formulation comprising the novel compounds disclosed herein is described. The formulation may include one or more components disclosed herein selected from the group consisting of: solvents, emitters, hosts, hole injection materials, hole transport materials, electron blocking materials, hole blocking materials, and electron transport materials.

[0337] This disclosure covers the chemical structure of any novel compound comprising this disclosure or its monovalent or multivalent variants. In other words, the compound of the present invention or its monovalent or multivalent variants may be part of a larger chemical structure. Such chemical structures may be selected from the group consisting of monomers, polymers, macromolecules, and supramolecular (also called supermolecules). As used herein, a “monovalent variant of a compound” refers to the same part of the compound, but in which one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a “multivalent variant of a compound” refers to the same part of the compound, but in which more than one hydrogen has been removed and replaced with one or more bonds to the rest of the chemical structure. In the case of supramolecular compounds, the compound of the present invention may also be incorporated into supramolecular complexes without covalent bonds. As used in this context, the description of structure A comprising part B means that structure A comprises the structure of part B, the structure of which does not include H or D atoms that can be attached to part B. This is because at least one H or D on a given part of the structure must be replaced with a substituent so that part B may be part of structure A, and after it becomes part of structure A, one or more of the H or D on the given part of the structure B may be further substituted.

[0338] C. OLEDs and devices disclosed herein

[0339] In another aspect, this disclosure also provides an OLED device comprising a first organic layer containing compounds as disclosed in the above compound portion of this disclosure.

[0340] In some embodiments, the OLED includes: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises Ir(L) as described herein. A ) x (L B ) y Compounds.

[0341] In some embodiments, the organic layer is selected from the group consisting of HIL, HTL, EBL, EML, HBL, ETL, and EIL. In some embodiments, the organic layer may be an emission layer and the compound as described herein may be an emission dopant or a non-emission dopant.

[0342] In some embodiments, the organic layer may further comprise a body, wherein the body comprises at least one chemical group selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, 5λ 2-Benzo[d]benzo[4,5]imidazo[3,2-a]imidazolium, 5,9-dioxa-13b-boronazona[3,2,1-de]anthracene, azacyclohexylborane, oxaborane, dihydroacridine, oxanthracene, dihydrobenzoazasilane, dibenzooxasiline, phenoxazine, phenoxthiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, borylalkyl, silylalkyl, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ 2 - benzo[d]benzo[4,5]imidazo[3,2-a]imidazo and aza-(5,9-dioxa-13b-boronanaphtho[3,2,1-de]anthracene).

[0343] In some embodiments, the subject may be selected from the group of structures in the following subject group 1:

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351] in:

[0352] Each of J1 to J6 is independently either C or N;

[0353] L' is a direct bond or an organic linking group;

[0354] Each Y AA Y BB Y CC and Y DD Independently select from the following groups: non-existent bond, direct bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, BRR';

[0355] R A' R B' R C' R D' RE' R F' and R G' Each of these terms independently represents monosubstituted, at most maximum substituted, or unsubstituted.

[0356] Each R, R', R A' R B' R C' R D' R E' R F' and R G' Substituents are independently hydrogen or selected from the group of general substituents as defined herein; any two substituents may join or fuse to form a ring;

[0357] Furthermore, where possible, each unsubstituted aromatic carbon atom can be replaced by one or more N atoms to form a nitrogen-substituted ring.

[0358] In some embodiments, at least one of J1 to J3 is N. In some embodiments, at least two of J1 to J3 are N. In some embodiments, all three of J1 to J3 are N. In some embodiments, each Y CC and Y DD Independently, it is O, S, or SiRR', or more preferably O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is substituted with N to form a nitrogen heterocycle.

[0359] In some embodiments, L' is an organic linking group 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.

[0360] In some embodiments, the subject is selected from the group consisting of: EG1-MG1-EG1 to EG53-MG27-EG53 having the formula EGa-MGb-EGc, or EG1-EG1 to EG53-EG53 having the formula EGa-EGc when MGb is absent, 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 to EG53 are shown below:

[0361]

[0362]

[0363] The structural diagrams of MG1 through MG27 are shown below:

[0364]

[0365] In the MGb structure shown above, the two bond positions in the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24 and MG25 are marked with numbers for identification purposes.

[0366] In some embodiments, the subject can be any of its nitrogen-substituted variants, its fully or partially deuterated variants, and combinations thereof. In some embodiments, the subject has the formula EGa-MGb-EGc and is selected from the group consisting of h1 to h112 as defined in the following list of subjects group 2, wherein each of MGb, EGa, and EGc is defined as follows:

[0367]

[0368]

[0369] In the table above, the EGa and EGc structures bonded to one of the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24 and MG25 are marked with a numerical prefix, which indicates their bond position in the MGb structure.

[0370] In some embodiments, the organic layer may further comprise a body, wherein the body comprises a metal complex.

[0371] In some embodiments, the emitter layer may comprise two bodies: a first body and a second body. In some embodiments, the first body is a hole transport body and the second body is an electron transport body. In some embodiments, the first body is a hole transport body and the second body is a bipolar body. In some embodiments, the first body is an electron transport body and the second body is a bipolar body. In some embodiments, the first body and the second body may form an excited-state complex. In some embodiments, the emitter layer may comprise a third body. In some embodiments, the third body is selected from the group consisting of: an insulating body (wide bandgap body), a hole transport body, and an electron transport body. In some embodiments, the third body forms an excited-state complex with one of the first body and the second body, or with both of the first body and the second body. In some embodiments, the emitter layer may comprise a fourth body. In some embodiments, the fourth body is selected from the group consisting of: an insulating body (wide bandgap body), a hole transport body, and an electron transport body. In some embodiments, the fourth body forms an excited-state complex with one of the first body, the second body, and the third body, with both of the first body, the second body, and the third body, or with each of the first body, the second body, and the third body. In some embodiments, the LUMO of the electron transport host is 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 HOMO of the hole transport host is greater than -5.6 eV, greater than -5.5 eV, greater than -5.4 eV, or greater than -5.35 eV. HOMO and LUMO values ​​can be determined using solution electrochemistry. Solution cyclic voltammetry and differential pulse voltammetry can be performed using a CH instrument model 6201B potentiostat, with anhydrous dimethylformamide (DMF) solvent and tetrabutylammonium hexafluorophosphate as the supporting electrolyte. Glassy carbon, platinum wire, and silver wire are used as the working electrode, counter electrode, and reference electrode, respectively. The electrochemical potential can be referenced to the internal ferrocene-ferrocene redox pair (Fc / Fc+) by measuring the peak potential difference using differential pulse voltammetry.According to the literature ((a) Fink R.; Heischkel Y.; Thelakkat M.; Schmidt H.-W.), Materials Chemistry (Chem. Mater.) 1998, 10, 3620-3625; (b) Pommerehne J.; Vestweber H.; Guss W.; Mahrt RF; Bassler H.; Porsch M. M.); Daub, Journal of Advanced Materials (J. Adv. Mater.) 1995, 7, 551), determined the corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies by measuring the redox potentials of cations and anions relative to a ferrocene reference (4.8 eV relative to vacuum).

[0372] In some embodiments, the compound described herein may be a sensitizer or a component of a sensitizer; wherein the device may further include a receptor that receives energy from the sensitizer. In some embodiments, the receptor is an emitter in the device. In some embodiments, the receptor may be a fluorescent material. In some embodiments, the compound described herein may be used as a phosphorescent sensitizer in an OLED, wherein one or more layers in the OLED contain receptors in the form of one or more non-delayed fluorescent and / or delayed fluorescent materials. In some embodiments, the compound described herein may be used as a component of an excited-state complex used as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to the receptor and the receptor to emit energy or further transfer energy to the final emitter. The receptor concentration may range from 0.001% to 99.9%. The receptor may be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the receptor is a thermally activated delayed fluorescence (TADF) material. In some embodiments, the receptor is a non-delayed fluorescent material. In some embodiments, emission may be generated by any one or all of the sensitizer, receptor, and final emitter. In some embodiments, the receptor emits at room temperature with a full width at half maximum (FWHM) equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. A narrower FWHM indicates better color purity for OLED display applications.

[0373] As used herein, phosphorescence generally refers to photon emission when the electron spin quantum number changes, i.e., the initial and final states of emission have different electron spin quantum numbers, such as from T1 to S0. Most Ir and Pt complexes currently used in OLEDs are phosphorescent emitters. In some embodiments, such excited-state complexes can also emit phosphorescence if the formation involves a triplet emitter. On the other hand, fluorescent emitters generally refer to photon emission when the electron spin quantum number remains constant, such as from S1 to S0 or from D1 to D0. Fluorescent emitters can be delayed or non-delayed fluorescent emitters. Depending on the spin state, fluorescent emitters can be singlet, doublet, or other multiplyt emitters. It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistical limit through delayed fluorescence. Two types of delayed fluorescence exist: P-type and E-type delayed fluorescence. P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA). On the other hand, E-type delayed fluorescence does not depend on the collision of two triplet states, but rather on the thermal population between the triplet and singlet excited states. Thermal energy can activate the triplet state to transition back to the singlet state. This type of delayed fluorescence is also known as TADF. E-type delayed fluorescence characteristics can be seen in excited-state complex systems or single compounds. Without being bound by theory, it is assumed that TADF emission requires a small singlet-triplet bandgap (ΔE) less than or equal to 400, 350, 300, 250, 200, 150, 100, or 50 meV. S-T These are compounds or excited-state complexes of electron transport compounds (TADFs). There are two main types of TADF emitters: one called donor-acceptor TADF and the other called multi-resonant (MR) TADF. Typically, single-compound donor-acceptor TADF compounds are constructed by connecting an electron donor moiety (such as an amino or carbazole derivative) and an electron acceptor moiety (such as an N-containing six-membered aromatic ring or a cyano-substituted aromatic ring). Donor-acceptor excited-state complexes can be formed between hole-transporting compounds and electron-transporting compounds. Examples of MR-TADF materials include highly conjugated fused-ring systems. In some embodiments, MR-TADF materials contain boron, carbon, and nitrogen atoms. Such materials may also contain other atoms, such as oxygen. In some embodiments, the reverse intersystem crossing time from T1 to S1 for delayed fluorescence emission at 293 K is less than or equal to 10 microseconds. In some embodiments, such a time can be greater than 10 microseconds and less than 100 microseconds.

[0374] In some embodiments, the OLED may include additional compounds selected from the group consisting of: non-delayed fluorescent materials, delayed fluorescent materials, phosphorescent materials, and combinations thereof.

[0375] In some embodiments, the compounds of the present invention described herein are phosphorescent materials.

[0376] In some embodiments, the phosphorescent material is an emitter that emits light within the OLED. In some embodiments, the phosphorescent material does not emit light within the OLED. In some embodiments, the phosphorescent material transfers its excited state to another material within the OLED. In some embodiments, the phosphorescent material participates in charge transport within 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 excited-state complex with another material within the OLED (e.g., a host material, an emitter material).

[0377] In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material is an emitter that emits light within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material does not emit light within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material transfers its excited state to another material within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material participates in charge transport within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material is an acceptor, and the OLED further includes a sensitizer.

[0378] In some embodiments of OLEDs, the delayed fluorescence material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescence material is a metal complex. In some embodiments, the delayed fluorescence material is a non-metallic complex. In some embodiments, the delayed fluorescence material is a Pt, Pd, Zn, Cu, Ag, or Au complex (some of which are also referred to as metal-assisted (MA)TADF). In some embodiments, the metal-assisted delayed fluorescence material comprises a metal-carbamate bond. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material comprises at least one chemical group selected from the group consisting of: arylamine, aryloxy, arylthio, triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazo, 5,9-dioxa-13b-boronazona[3,2,1-de]anthracene, 5λ 2 ,9λ 2 -diaza-13b-boronanaphene[2,3,4-de]anthracene, 5-oxa-9λ 2-aza-13b-boronazonaphtho[3,2,1-de]anthracene, azacyclohexylborane, oxaborane, dihydroacridine, oxanthracene, dihydrobenzoazasilane, dibenzooxasilane, phenoxazine, phenoxthiazine, dihydrophenoxazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, borane, amino, silane, their aza variants and combinations thereof. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material comprises tri(aryl / heteroaryl)borane, wherein one or more pairs of substituents from the aryl / heteroaryl group are bonded to form a ring. In some embodiments, the fluorescent material comprises at least one chemical group selected from the group consisting of: naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azurite.

[0379] In another aspect, the OLED of this disclosure may also include an emitting region containing a compound or formulation of a compound as disclosed in the foregoing compound portion of this disclosure. In some embodiments, the emitting region may contain Ir(L) as described herein. A ) x (L B ) y The compound or formulation containing said compound. In some embodiments, the emission region comprises one or more organic layers, wherein at least one of said one or more organic layers has a minimum thickness selected from the group consisting of: 350, 400, 450, 500, 550, 600, 650 and In some embodiments, at least one of the one or more organic layers is formed by an emission system having a figure of merit (FOM) equal to or greater than a value 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 formulation of a compound as disclosed in Parts A and D of this disclosure.

[0380] In some embodiments, the OLED or emitting region comprising the compound of the present invention disclosed herein may be incorporated into a full-color pixel arrangement of a device. Such a full-color pixel arrangement of a device comprises at least one pixel, wherein the at least one pixel comprises a first sub-pixel and a second sub-pixel. The first sub-pixel comprises a first OLED, which comprises a first emitting region. The second sub-pixel comprises a second OLED, which comprises a second emitting region. In some embodiments, the first and / or second OLEDs, the first and / or second emitting regions may be the same or different and may each independently have various device features and embodiments comprising the compound of the present invention, as well as various combinations and sub-combinations of various device features and embodiments comprising the compound of the present invention, as disclosed herein.

[0381] In some embodiments, the first emission region is configured to emit light with a peak wavelength λ. max1 The second emission region is configured to emit light with a peak wavelength λ. max2 The light. In some embodiments, the peak wavelength λ max1 With λ max2 The difference between them is at least 4 nm but within the same color. For example, light blue and dark blue light as described above. In some embodiments, the first emission region is configured to emit light with a peak wavelength λ in one region of the visible spectrum at 400-500 nm, 500-600 nm, or 600-700 nm. max1 The light emitted; and the second emission 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, and 600-700 nm. max2 The light emitted. In some embodiments, the first emitting region comprises (if more than one) a first number of emitting layers deposited on the other; and the second emitting region comprises (if more than one) a second number of emitting layers deposited on the other; and the first number is different from the second number. In some embodiments, both the first emitting region and the second emitting region comprise phosphorescent materials that may be the same or different. In some embodiments, the first emitting region comprises phosphorescent material, while the second emitting region comprises fluorescent material. In some embodiments, both the first emitting region and the second emitting region comprise fluorescent materials that may be the same or different.

[0382] In some embodiments, at least one pixel of an OLED or emitting region comprises a total of N sub-pixels; wherein the N sub-pixels include a first sub-pixel and a second sub-pixel; wherein each of the N sub-pixels includes an emitting region; wherein the total number of emitting regions within at least one pixel is equal to or less than N-1. In some embodiments, the second emitting region is identical to the first emitting region; and each sub-pixel of at least one pixel includes an emitting region identical to the first emitting region. In some embodiments, a full-color pixel arrangement may have multiple pixels including a first pixel region and a second pixel region; wherein at least one display feature in the first pixel region differs from a corresponding display feature in the second pixel region, and wherein the at least one display feature is selected from the group consisting of: resolution, cavity mode, color, external coupling, and color filter.

[0383] In some embodiments, the OLED is a stacked OLED comprising one or more charge generating layers (CGLs). In some embodiments, the OLED comprises a first electrode, a first emitting region disposed above the first electrode, a first CGL disposed above the first emitting region, a second emitting region disposed above the first CGL, and a second electrode disposed above the second emitting region. In some embodiments, the first emitting region and / or the second emitting region may have various device features as described above for pixelation devices. In some embodiments, the stacked OLED is configured to emit white. In some embodiments, one or more of the emitting regions in the pixelated OLED or stacked OLED comprise a sensitizer and an acceptor having various sensitization device features and various embodiments of the compounds of the present invention disclosed herein. For example, the first emitting region is included in a sensitization device while the second emitting region is not included in a sensitization device; in some cases, both the first and second emitting regions are included in a sensitization device.

[0384] In some embodiments, the OLED can emit light from plasmonic modes having at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99%, or 100% light intensity. In some embodiments, at least one of the anode, cathode, or a new layer disposed above the organic emitting layer serves as a reinforcement layer. The reinforcement layer comprises a plasmonic material exhibiting surface plasmon resonance, which is nonradiatively coupled to the emitter material and transfers excited-state energy from the emitter material to the nonradiative mode of the surface plasmon polaritons. In some embodiments, the reinforcement layer is positioned at a distance from the organic emitting layer not exceeding a threshold distance, wherein the emitter material has a total nonradiative decay rate constant and a total radiative decay rate constant due to the presence of the reinforcement layer. The threshold distance is the position where the total nonradiative decay rate constant equals the total radiative decay rate constant. Another threshold distance is the distance at which the total radiative decay rate constant divided by the sum of the total nonradiative decay rate constant and the total radiative decay rate constant equals the photoluminescence yield of the emitting material without the reinforcement layer.

[0385] In some embodiments, the OLED further includes an external coupling layer. In some embodiments, the external coupling layer is disposed above the enhancement layer on the side opposite the organic emitting layer. The external coupling layer scatters energy from surface plasmon polaritons. In some embodiments, this energy is scattered as photons into free space. In other embodiments, energy is scattered from the surface plasmon polariton modes of the device into other modes, such as, but not limited to, organic waveguide modes, substrate modes, or another waveguide mode. In some embodiments, one or more intermediary layers may be disposed between the enhancement layer and the external coupling layer. Examples of intermediary layers may be dielectric materials, including organic, inorganic, perovskite, and oxide materials, and may comprise stacks and / or mixtures of these materials.

[0386] The enhancement layer alters the effective properties of the medium in which the emitter material resides, thereby causing any or all of the following: reduced emissivity, altered emission profile, changes in emission intensity with angle, altered emitter material stability, altered OLED efficiency, and reduced roll-off efficiency of the OLED device. Placing the enhancement layer on the cathode side, anode side, or both sides, or placing the enhancement layer itself as a CGL, produces an OLED device that utilizes any of the aforementioned effects. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLED according to this disclosure may also include any other functional layers commonly found in OLEDs.

[0387] In some embodiments, the reinforcing layer may comprise a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. In some embodiments, the plasmonic material comprises at least one metal. In such embodiments, the metal may comprise at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, or Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the reinforcing layer is configured as a planar layer. In other embodiments, the reinforcing layer is characterized by wavelengths arranged periodically, quasi-periodically, or randomly, or by subwavelengths arranged periodically, quasi-periodically, or randomly.

[0388] In some embodiments, the outer coupling layer has a wavelength or subwavelength characteristic of being arranged periodically, quasi-periodically, or randomly. In some embodiments, the outer coupling layer may be composed of a plurality of nanoparticles. In some embodiments, the outer coupling layer is composed of a plurality of nanoparticles disposed on a material. In these embodiments, the outer coupling layer can be adjusted by at least one of the following: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, adding an additional layer disposed on the plurality of nanoparticles, changing the thickness of a reinforcing layer, or changing the material of a reinforcing layer. The plurality of nanoparticles of the device may be formed from at least one of the following: metal, dielectric material, semiconductor material, metal alloy, mixture of dielectric materials, stack or layer of one or more materials and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the outer coupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the outer coupling layer is formed by photolithography.

[0389] In some embodiments of the plasmonic device, the emitter and / or host compound used in the emitter layer has a vertical dipole ratio (VDR) of 0.33 or greater. In some such embodiments, the emitter and / or host compound has a VDR of 0.40, 0.50, 0.60, 0.70 or greater.

[0390] In another aspect, this 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 compounds or formulations of compounds as disclosed in the above compound section of this disclosure.

[0391] In some embodiments, the consumer product includes an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise Ir(L) as described herein. A ) x (L B ) y Compounds.

[0392] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to both the anode and cathode. When a current is applied, holes are injected into the anode and electrons into the organic layer from the cathode. The injected holes and electrons migrate toward their respective oppositely charged electrodes. When electrons and holes are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. When the exciton relaxes through a photoemission mechanism, light is emitted. In some cases, excitons can be localized as excimers or excited-state complexes. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0393] Figure 1 An organic light-emitting device 100 is shown. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer (HIL) 120, a hole transport layer (HTL) 125, an electron blocking layer (EBL) 130, an emission 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 blocking layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by sequentially depositing the layers. The properties and functions of these various layers, as well as the example materials, are described in more detail in columns 6-10 of US 7,279,704, which is incorporated herein by reference.

[0394] Further examples of each of these layers are available. For instance, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a 50:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of luminescent and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of cathodes, comprising composite cathodes having a thin layer of metal (e.g., Mg:Ag) having an overlying transparent, conductive, sputtered ITO layer, are disclosed in their entirety in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety. Theories and uses of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated herein by reference in their entirety. Examples of implantation layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. Descriptions of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0395] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emitter layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by sequentially depositing these layers. Because the most common OLED configuration has a cathode disposed above the anode, and the device 200 has a cathode 215 disposed below the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the corresponding layers of the device 200. Figure 2 Provide an example of how some layers can be omitted from the structure of device 100.

[0396] Figure 1 and 2The simple layered structures described herein are provided by way of non-limiting examples, and it should be understood that embodiments of this disclosure can be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. Functional OLEDs can be obtained by combining the various layers described in different ways, or the layers can be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many examples provided herein describe various layers as comprising a single material, it should be understood that combinations of materials, such as mixtures of host and dopant, or more generally, mixtures, can be used. Furthermore, the layers may 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 emitter layer 220, and can be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise, for example, regarding Figure 1 and 2 Multiple layers of the different organic materials mentioned above.

[0397] Structures and materials not specifically described can also be used, such as OLEDs (PLEDs) containing polymeric materials, as disclosed in, for example, U.S. Patent No. 5,247,190 to Friend et al., which is incorporated herein by reference in its entirety. By another example, OLEDs with a single organic layer can be used. OLEDs can be stacked, for example, as described in, U.S. Patent No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. OLED structures can be deviated from... Figure 1 and 2 The simple layered structure described herein. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as the tabletop structure described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the recessed structure described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated herein by reference in their entirety.

[0398] Unless otherwise specified, any of the layers in the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet printing (as described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated herein by reference in their entirety), organic vapor deposition (OVPD) (as described in U.S. Patent No. 6,337,102 by Forrest et al., which are incorporated herein by reference in their entirety), and deposition via organic vapor jet printing (OVJP, also known as organic vapor jet deposition (OVJD)) (as described in U.S. Patent No. 7,431,968, which is incorporated herein by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation, sputtering, chemical vapor deposition, atomic layer deposition, and electron beam deposition. Preferred patterning methods include patterning via mask deposition, photolithography, and cold soldering (as described in U.S. Patents 6,294,398 and 6,468,819, which are incorporated herein by reference in their entirety) and some of the methods associated with deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods may also be used. The material to be deposited may be modified to suit a particular deposition method. For example, branched or unbranched substituents, preferably containing at least three carbons, such as alkyl and aryl groups, may be used in small molecules to enhance their solution handling ability. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. Materials with asymmetric structures may have better solution handling ability than materials with symmetric structures because asymmetric materials may have a lower tendency to recrystallize. Dendritic polymer substituents may be used to enhance the solution handling ability of small molecules.

[0399] The device manufactured according to embodiments of this disclosure may optionally further include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage caused by exposure to harmful substances in an environment including moisture, vapor, and / or gases. The barrier layer may be deposited on, under, or beside a substrate or electrode, or on any other part of the device, including edges. The barrier layer may comprise a single layer or multiple layers. The barrier layer can be formed using various known chemical vapor deposition techniques and may comprise 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 contain inorganic compounds or organic compounds, or both. Preferred barrier layers comprise multiple alternative layers of materials including: polymeric and nonpolymeric materials; organic and inorganic materials; or mixtures of polymeric and nonpolymeric materials, an example of which is described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety.

[0400] The apparatus manufactured according to embodiments of this disclosure can be incorporated into a wide variety of electronic component modules (or units), which can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include displays, lighting devices (such as discrete light source devices or lighting panels), etc., which can be utilized by end-user product manufacturers. The electronic component module may optionally include driving electronics and / or a power supply. The apparatus manufactured according to embodiments of this disclosure can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. A consumer product incorporating an OLED is disclosed, wherein the OLED includes compounds of this disclosure in its organic layer. The consumer product should include any type of product containing one or more light sources and / or one or more of some type of visual display. Examples of the consumer products described include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular phones, tablet computers, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple tiled displays, theater or stadium screens, phototherapy devices, and signage. Various control mechanisms, including passive and active matrices, can be used to control the devices manufactured according to this disclosure. Many of the devices are intended for use in temperature ranges comfortable for humans, such as 18°C ​​to 30°C, and more preferably at room temperature (20-25°C), but can be used outside this temperature range (e.g., -40°C to +80°C).

[0401] Further details regarding OLEDs and the definitions described above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0402] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can utilize the materials and structures described herein. More generally, organic devices such as organic transistors can utilize the materials and structures described herein.

[0403] In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer including carbon nanotubes. In some embodiments, the OLED further comprises one or more quantum dots. Such quantum dots may be in the emission layer or in other functional layers, such as conversion layers.

[0404] In some embodiments, the OLED comprises an RGB pixel arrangement or a white pixel arrangement with a color filter. 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 with 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 with 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.

[0405] D. Other materials used in OLEDs

[0406] The materials described herein are various examples of materials that can be used in specific layers in OLEDs. They can also be used in combination with a wide variety of other materials present in the device. For example, the emission dopants disclosed herein can be used by the emission dopants themselves in the EML, or in combination with a wide variety of other emitters, hosts, transport layers, barrier layers, implantation layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds and devices disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0407] a) Conductive dopants:

[0408] Charge transport layers can be doped with conductive dopants to substantially alter their charge carrier density, which in turn changes their conductivity. Conductivity is increased by generating charge carriers in the matrix material and, depending on the type of dopant, can also achieve changes in the Fermi level of the semiconductor. Hole transport layers can be doped with p-type conductive dopants, and n-type conductive dopants are used in electron transport layers. 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 extended by acyclic double bonds.

[0409] b) HIL / HTL:

[0410] The hole injection / transport materials used in this disclosure are not particularly limited, and any compound may be used, provided that the compound is commonly used as a hole injection / transport material. Examples of materials include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indole-carbazole derivatives; polymers containing fluorinated hydrocarbons; polymers with conductive dopants; conductive polymers, such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; and metal oxide derivatives, such as MoO. x p-type semiconductive organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylhexacarbonitrile; metal complexes; and crosslinkable compounds.

[0411] Examples of aromatic amine derivatives used for HIL or HTL include (but are not limited to) the following general structures:

[0412]

[0413] Ar 1 To Ar 9 Each of these is selected from the group consisting of, for example, aromatic hydrocarbon cyclic compounds such as: benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, fenene, fluorene, pyrene, Perylene and azurite; the group consisting of, for example, aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridinylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, inoxazine, benzoxazole, benziisoxazole, benzothiazole, quinoline, isoquinoline, zoline, quinazoline Quinoxaline, naphthidine, phthalazine, pteridine, oxanthracene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenepyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units, said cyclic structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. 1 To Ar 9 Each of them can be unsubstituted or can be substituted by the general substituents described above, and any two substituents can be joined or fused into a ring.

[0414] In some embodiments, each Ar 1 To Ar 9 Independently includes portions selected from the following groups:

[0415]

[0416] Where k is an integer from 1 to 20; X 101 To X 108 It is C or N; Z 101 It is C, N, O, or S.

[0417] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0418] Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 The coordinating atoms are independently selected from C, N, O, P, and S; L 101 It 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.

[0419] In some embodiments, (Y) 101 -Y 102 (Y) is a 2-phenylpyridine or 2-phenylimidazole derivative. In some embodiments, (Y) 101 -Y 102 Met is a carbene ligand. In some embodiments, Met is selected from Ir, Pt, Pd, Os, Cu, and Zn. In some embodiments, the metal complex has a relative... + The minimum oxidation potential in solution with / Fc coupling is less than about 0.6V.

[0420] In some embodiments, the HIL / HTL material is selected from the group consisting of: phthalocyanine and porphyrin compounds, starburst triarylamine, CF x Fluorinated hydrocarbon polymers, conductive polymers (e.g., PEDOT:PSS, polyaniline, polythiophene), phosphonic acids and silane SAMs, triarylamines or polythiophene polymers containing conductive dopants, organic compounds containing conductive inorganic compounds (such as molybdenum oxide and tungsten oxide), n-type semiconductive organic complexes, organometallic complexes, crosslinkable compounds, polythiophene-based polymers and copolymers, triarylamines, triarylamines containing spirofluorene cores, arylamine carbazole compounds, triarylamines containing (di)benzothiophene / (di)benzofuran, indole-carbazole, isoindole compounds, and metal carbene complexes.

[0421] c) EBL:

[0422] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emitter layer. The presence of such a blocking layer in a device can result in generally higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, the blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy compared to one or more emitters closest to the EBL interface. In some embodiments, the compound used in the EBL contains 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 of the bodies in the EML. In some embodiments, the compound used in the EBL contains the same molecule or the same functional groups as those used in one of the bodies described below.

[0423] d) Main body:

[0424] The light-emitting layer of the organic EL device disclosed herein preferably contains at least a light-emitting material as a dopant and a host material. Examples of the host material are not particularly limited, and any metal complex or organic compound can be used, as long as the host does not completely quench the emission of the dopant.

[0425] Examples of metal complexes used as the host preferably have the following general formula:

[0426]

[0427] Where Met is a metal; (Y) 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104 The coordinating atoms are independently selected from C, N, O, P, and S; L 101 It 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.

[0428] In some embodiments, the metal complex is:

[0429]

[0430] (ON) is a bidentate ligand of a metal that coordinates with O and N atoms.

[0431] In some embodiments, Met is selected from Ir and Pt. In another embodiment, (Y 103 -Y 104 ) is a carbaene ligand.

[0432] In some embodiments, the host compound contains at least one selected from the group consisting of, for example, aromatic hydrocarbon cyclic compounds such as: benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, fenene, fluorene, pyrene, etc. Perylene and azurite; the group consisting of, for example, aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenene, furan, thiophene, benzofuran, benzothiophene, benzoselenene, carbazole, indolocarbazole, pyridinylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, Oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benziisoxazole, benzothiazole, quinoline, isoquinoline, cinnamoline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, oxanthracene, acridine, phenazine, phenothiazine, phenothiazine, 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]imidazolium, 5,9-dioxa-13b-boronazonaphtho[3,2,1-de]anthracene; and groups consisting of 2 to 10 cyclic structural units, said cyclic structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. Each option within each group may be unsubstituted or may be substituted with universal substituents as described herein or may be further fused.

[0433] In some embodiments, the host compound comprises at least one portion selected from the group consisting of: Where k is an integer between 0 and 20 or between 1 and 20. X 101 To X 108 Independently selected from C or N. Z 101 and Z 102 It is independently selected from C, N, O, or S.

[0434] In some embodiments, the host material is selected from the group consisting of: arylcarbazoles, metal 8-hydroxyquinoline compounds (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorene), aromatic fused rings, zinc complexes, and based on... Compounds, aryltriphenylene compounds, polyfused heteroaryl compounds, donor-acceptor molecules, dibenzofuran / dibenzothiophene compounds, polymers (e.g., PVK), spirofluorene compounds, spirofluorene-carbazole compounds, indole-carbazole, 5-membered electron-deficient heterocycles (e.g., triazoles, oxadiazoles), tetraphenylene complexes, metal phenoxypyridine compounds, metal coordination complexes (e.g., Zn, Al containing N^N ligands), dibenzothiophene / dibenzofuran-carbazole compounds, silicon / germanium aryl compounds, aryl benzoyl esters, non-conjugated carbazoles, aza-carbazole / dibenzofuran / dibenzothiophene compounds, and high triplet state organometallic complexes (e.g., metal-carbaene complexes).

[0435] e) Emitter material in EML:

[0436] One or more emitter materials may be used in conjunction with the compounds or devices disclosed herein. The emitter materials may be emittant or non-emittent in current devices as described herein. Examples of emitter materials are not particularly limited, and any compound may be used as long as it is capable of generating emission in a conventional OLED device. Examples of suitable emitter materials include, but are not limited to, compounds capable of generating emission via phosphorescence, non-delayed fluorescence, delayed fluorescence (especially thermally activated delayed fluorescence, i.e., TADF (also known as E-type delayed fluorescence)), triplet-triplet annihilation, or combinations thereof.

[0437] In some embodiments, the emitter material has the formula M(L) 1 ) x (L 2 ) y (L 3 ) z ;

[0438] Where L 1 L 2 and L 3 They can be the same or different;

[0439] Where x is 1, 2, or 3;

[0440] Where y is 0, 1, or 2;

[0441] Where z is 0, 1, or 2;

[0442] Where x+y+z is the oxidation state of the metal M;

[0443] Where L 1 Select the group consisting of structures from the following list of ligands:

[0444]

[0445]

[0446]

[0447] Each L 2 and L 3 Independent freedom of choice The group consisting of structures in the ligand list; where:

[0448] M is selected from the following groups: Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu;

[0449] T can be freely selected from the following groups: B, Al, Ga, and In;

[0450] K 1' It is a direct key or a selection of the following groups: NR e PR e , O, S and Se;

[0451] Each Y 1 To Y 15 Independently select groups composed of free carbon and nitrogen;

[0452] Y' selects from the following groups: BR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f SiR e R f and GeR e R f ;

[0453] Each R a R b R c and R d It can independently represent monosubstituted to the maximum possible number of substitutions or no substitution;

[0454] Each R a1 R b1 R c1 R d1 R a R b R c R d R e and R f Substituents that are independently hydrogen or selected from the group of universal substituents as defined herein; and

[0455] Any two of the substituents can fused or joined to form a ring or a polydentate ligand.

[0456] In some embodiments, the emitter material is selected from the group consisting of the following dopant group 1:

[0457]

[0458]

[0459]

[0460]

[0461]

[0462] in

[0463] X 96 To X 99 Each of them is independently C or N;

[0464] Each Y 100 Independently select the groups composed of NR", O", S and Se;

[0465] R 10a R 20a R 30a R 40a and R 50a Each of these terms independently represents monosubstituted, at most maximum substituted, or unsubstituted.

[0466] 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 them is independently hydrogen or a substituent selected from the group of general substituents defined herein; any two substituents may join or fuse to form a ring.

[0467] In some embodiments, the emitter material is selected from the group consisting of the following dopant group 2:

[0468]

[0469]

[0470]

[0471]

[0472]

[0473]

[0474]

[0475]

[0476] in:

[0477] Each Y 100 Independently select the groups composed of NR", O", S and Se;

[0478] L is independently selected from the following groups: 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;

[0479] X 100 and X 200 Each time it appears, select from the following groups: O, S, Se, NR” and CR”R”';

[0480] Each R A” R B” R C” R D” R E” and R F” Independently represent monosubstituted, at most maximum substituted, or unsubstituted;

[0481] 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 them is independently hydrogen or a substituent selected from the group of general substituents as defined herein; and any two substituents may join or fuse to form a ring.

[0482] In some embodiments of dopant groups 1 and 2 above, each unsubstituted aromatic carbon atom may be replaced by N to form a nitrogen heterocycle. In some embodiments, the maximum number of N atoms in a ring is 1 or 2. In some embodiments of dopant group 2 above, each Pt atom in the formula may be replaced by a Pd atom.

[0483] In some embodiments of OLEDs, the delayed fluorescence material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescence material is a metal complex. In some embodiments, the delayed fluorescence material is a non-metallic complex. In some embodiments, the delayed fluorescence material is a Zn, Cu, Ag, or Au complex.

[0484] In some embodiments of OLEDs, the delayed fluorescence material has the formula M(L 5 (L) 6 ), where M is Cu, Ag, or Au, L 5 and L 6 Different, and L 5 and L 6 Choose independently from the following groups:

[0485]

[0486]

[0487] Where A 1 -A 9 Each is independently selected from C or N;

[0488] Each R P R Q and R U Independently represent monosubstituted, at most maximum substituted, or unsubstituted;

[0489] Each R P R P R U R SA R SB R RA R RB R RC R RD R RE and R RF Substituents are independently hydrogen or selected from the group of general substituents as defined herein; any two substituents may join or fuse to form a ring.

[0490] In some embodiments of the OLED, the delayed fluorescence material comprises at least one donor portion selected from the group consisting of:

[0491]

[0492] Where Y T Y U Y V and Y W Each of the following groups is selected independently: B, C, Si, Ge, N, P, O, S, Se, C=O, S=O, and SO2.

[0493] In some of the above embodiments, any carbon ring atom in each benzene ring of any of the above structures, up to a total of up to three carbon ring atoms, together with their substituents, may be replaced by N.

[0494] In some embodiments, the delayed fluorescence 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 donor moiety as described herein may be directly linked via a conjugated linker group or a non-conjugated linker group (such as sp...). 3 (Carbon or silicon atoms) are linked together.

[0495] In some embodiments, the fluorescent material comprises at least one chemical moiety selected from the group consisting of:

[0496]

[0497]

[0498]

[0499] Where Y F Y G Y H and Y I Each of the following groups can be selected independently: B, C, Si, Ge, N, P, O, S, Se, C=O, S=O, and SO2;

[0500] Where X F and X G Each group is independently selected from the groups composed of C and N.

[0501] In some of the above embodiments, any carbon ring atom in each benzene ring of any of the above structures, up to a total of up to three carbon ring atoms, together with their substituents, may be replaced by N.

[0502] f)HBL:

[0503] Hole blocking layers (HBLs) can be used to reduce the number of holes and / or excitons leaving the emitter layer. The presence of such blocking layers in a device can result in generally higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, blocking layers can be used to confine emission to the desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (farthest from vacuum level) and / or higher triplet energy compared to one or more emitters closest to the HBL interface.

[0504] In some embodiments, the compounds used in HBL contain the same molecules or the same functional groups as those used in the main body described above.

[0505] In some embodiments, the compound used in HBL comprises at least one of the following portions selected from the group consisting of:

[0506] Where k is an integer from 1 to 20; L 101 It is another ligand, and k' is an integer from 1 to 3.

[0507] g)ETL:

[0508] An electron transport layer (ETL) may comprise a material capable of transporting electrons. The ETL may be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used, provided it is typically used for electron transport.

[0509] In some embodiments, the compounds used in the ETL contain at least one of the following portions in their molecules:

[0510] and fullerenes; where k is an integer from 1 to 20, X 101 To X 108 Selected from C or N; Z 101 Choose a group consisting of C, N, O, and S.

[0511] In some embodiments, the metal complexes used in the ETL contain, but are not limited to, the following general formula:

[0512]

[0513] Wherein (ON) or (NN) are bidentate ligands of metals that coordinate with atoms O, N, or N,N; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bonded to the metal.

[0514] In some embodiments, the ETL material is selected from the group consisting of: anthracene-benzimidazole compounds, azirtriene derivatives, anthracene-benzothiazole compounds, metal 8-hydroxyquinoline compounds, metal hydroxybenzoquinoline compounds, bathocuprine compounds, 5-membered electron-deficient heterocycles (e.g., triazoles, oxadiazoles, imidazoles, benzimidazoles), thiophene compounds, arylborane compounds, fluorinated aromatic compounds, fullerenes (e.g., C60), triazine complexes, and Zn(N^N) complexes.

[0515] h) Charge Generation Layer (CGL)

[0516] In tandem or stacked OLEDs, the conduction layer (CGL) plays a fundamental role in performance. It consists of an n-doped layer and a p-doped layer, respectively, for injecting electrons and holes. Electrons and holes are supplied by the CGL and the electrodes. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials contain n- and p-conductive dopants used in the transport layer.

[0517] In any of the compounds disclosed herein, hydrogen atoms may be partially or completely deuterated. The minimum amount of deuterated hydrogen in a compound is selected from the group consisting of: 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. As used herein, the percentage of deuteration has its general meaning and includes the percentage of all possible hydrogen and deuterium atoms replaced by deuterium atoms. In some embodiments, the deuterium atom is attached to an aromatic ring. In some embodiments, the deuterium atom is attached to a saturated carbon atom, such as an alkyl or cycloalkyl carbon atom. In some other embodiments, the deuterium atom is attached to a heteroatom, such as a Si or Ge atom.

[0518] It should be understood that the various embodiments described herein are merely examples and are not intended to limit the scope of the invention. For instance, many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. The claimed invention may therefore include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that various theories regarding why the invention works are not intended to be limiting.

[0519] E. Experimental Data

[0520] Material Synthesis

[0521] Synthesis of 5-(methyl-d3)-2-(4-(trimethylsilyl)phenyl)pyridine (2)

[0522]

[0523] Potassium carbonate (75.40 g, 2.634 equivalents, 545.6 mmol) in water (80 mL) was added to 2-chloro-5-methylpyridine (26.89 g, 23.00 mL, 1.018 equivalents, 210.8 mmol) and (4-(trimethylsilyl)phenyl)boronic acid (40.20 g, 1 equivalent, 207.1 mmol) in 1,4-dioxane (400 mL). The mixture was evacuated and backfilled with N2 (three times), followed by the addition of tetra(triphenylphosphine)palladium(0) (14.00 g, 0.05850 equivalents, 12.12 mmol). The reaction mixture was stirred at 100 °C for 18 h, then cooled to room temperature (approximately 23 °C). The solvent was removed under vacuum, and the crude product was purified by column chromatography, eluting with 0%–10% ethyl acetate in heptane. The resulting product was deuterated and converted into 5-(methyl-d3)-2-(4-(trimethylsilyl)phenyl)pyridine (10.12 g, 20%), which was a colorless solid.

[0524] Synthetic compound 3

[0525]

[0526] A solution of 5-(methyl-d3)-2-(4-(trimethylsilyl)phenyl)pyridine 2 (15.8 g, 65 mmol, 2 equivalents) and iridium(III) chloride hydrate (12 g, 32 mmol, 1.0 equivalents) in 2-ethoxyethanol (240 mL) and deionized ultrafiltered (DIUF) water (80 mL) was heated at 90 °C for 90 h. After cooling to room temperature (about 23 °C), methanol (200 mL) was added to the mixture, and the suspension was filtered. The solid was washed with methanol and then dried in a vacuum oven at about 50 °C for three h to give 3 (17.5 g, 76% yield) as a yellow solid.

[0527] Example 1 of the invention

[0528]

[0529] A solution of 3 (10.00 g, 1 equivalent, 6.998 mmol), 1-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-2-(7-phenyldibenzo[b,d]furan-4-yl)-1H-benzo[d]imidazolium 4 (7.935 g, 1.9 equivalent, 13.30 mmol), and potassium acetate (2.060 g, 3.0 equivalent, 20.99 mmol) in dimethylformamide (DMF) (58 mL) and 2-ethoxyethanol (58 mL) was bubbled under nitrogen for 10 min. The reaction mixture was heated at 140 °C under an inert atmosphere for 3 h. The crude reactant was diluted with tetrahydrofuran (THF) (420 mL). The solution was then bubbled under nitrogen for 10 min and photoisomerized at 80 °C for 3 h. The crude compound was purified by silica gel chromatography and eluted with 50% toluene in hexane to obtain Example 1 of the present invention (2.2 g, 25% yield) as a yellow solid.

[0530] Synthesis Comparison Example 1

[0531]

[0532] A solution of 5 (7.00 g, 1 equivalent, 6.139 mmol), 1-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-2-(7-phenyldibenzo[b,d]furan-4-yl)-1H-benzo[d]imidazolium 4 (7.693 g, 2.1 equivalent, 12.89 mmol), and potassium acetate (1.807 g, 3.0 equivalent, 18.42 mmol) in DMF (50 mL) and 2-ethoxyethanol (50 mL) was bubbled under nitrogen for 10 minutes. The reactants were heated at 135 °C under an inert atmosphere for 4 hours. The crude reactants were diluted with THF (720 mL). The solution was then bubbled under nitrogen for 10 minutes and photoisomerized at 80 °C for 3 hours. The crude compound was purified by silica gel chromatography and eluted with 50% toluene in hexane to give Comparative Example 1 (12 g, 44% yield) as a yellow solid.

[0533] Synthesis of 5-chloro-2-phenylpyridine (7)

[0534]

[0535] Triphenylphosphine (2.73 g, 0.10 equivalent, 10.4 mmol) and palladium diacetate (1.17 g, 0.05 equivalent, 5.2 mmol) were added to a solution of 2-bromo-5-chloropyridine 6 (20.0 g, 104 mmol, 1 equivalent), phenylboronic acid (15.2 g, 1.2 equivalent, 125 mmol), and potassium carbonate (35.9 g, 2.5 equivalent, 260 mmol) in dimethoxyethane (DME) (205 mL) and water (133 mL). The mixture was heated in an oil bath at 90 °C for 18 hours. The reaction mixture was cooled and diluted with ethyl acetate (EtOAc) (1 L) and water (500 mL). The layers were separated, and the aqueous layer was extracted with EtOAc (250 mL). The combined organic layers were washed with water (250 mL), dried over MgSO4, filtered, and evaporated to give the crude substance. The crude substance was purified by silica gel chromatography to obtain compound 7 (19.0 g, 80%), which was a white solid.

[0536] Synthetic compound 8

[0537]

[0538] SPhos Pd G2 (4.5 g, 0.10 equivalent, 6.2 mmol) was added to a solution of 5-chloro-2-phenylpyridine 7 (11.80 g, 62.2 mmol, 1 equivalent) in THF (250 mL), followed by the addition of a solution of 1-adamantyl zinc bromide (0.5 M in THF, 150 mL, 1.20 equivalent, 75.0 mmol). The mixture was then heated in an oil bath at 60 °C for 3 hours. The resulting mixture was cooled and quenched with saturated NH4Cl (100 mL). EtOAc (1 L) and water (200 mL) were added, and the layers were separated. The organic layer was washed with water (100 mL), dried (MgSO4), filtered, and evaporated to give the crude substance. The crude substance was purified by silica gel chromatography to give compound 8 (9.9 g, 55%) as a white solid.

[0539] Synthetic compound 9

[0540]

[0541] A solution of 5-((3r,5r,7r)-adamantyl-1-yl)-2-phenylpyridine 8 (2.000 g, 4 equivalents, 6.910 mmol) and iridium(III) chloride hydrate (1.405 g, 2 equivalents, 3.455 mmol) in 2-ethoxyethanol (55 mL) and deionized ultrafiltered (DIUF) water (14 mL) was heated at 100 °C for 18 hours. After cooling to room temperature (about 23 °C), methanol (10 mL) was added to the mixture, and the suspension was filtered. The solid was washed with methanol and then dried in a vacuum oven at about 50 °C for three hours to give compound 9 (2.26 g, 81% yield) as a yellow solid.

[0542] Synthetic compound 10

[0543]

[0544] A solution of silver trifluoromethanesulfonate (I) (794.9 mg, 1.1 equivalents, 3.094 mmol) in methanol (12 mL) was added to a solution of compound 9 (2.260 g, 0.5 equivalents, 1.406 mmol) in dichloromethane (59 mL). The reaction mixture was stirred at room temperature for 18 hours, followed by filtration through a diatomaceous earth mat (diatomaceous earth). The mat was then washed with dichloromethane (50 mL). The filtrate was concentrated under reduced pressure, and the residue was dried overnight in a vacuum oven at 60 °C to give compound 10 (1.120 g, 1.140 mmol, 40.54%) as a yellow solid.

[0545] Example 2 of the present invention

[0546]

[0547] To a suspension of 10 (0.960 g, 1 equivalent, 977 μmol) and 1-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-2-(phenanthro[3,2-b]benzofuran-11-yl)-1H-benzo[d]imidazole 11 (789 mg, 1.3 equivalent, 1.27 mmol) in 2-ethoxyethanol (20 mL), 2,6-dimethylpyridine (209 mg, 227 μL, 2.0 equivalent, 1.95 mmol) was added. The mixture was heated to 100 °C for 48 hours. The resulting mixture was removed from the heat and allowed to cool to room temperature. The crude product was purified by silica gel chromatography, eluting with 70% toluene in heptane. The eluates containing the product were combined and concentrated under reduced pressure. The solid was dried in a vacuum oven at 50°C for 3 hours to obtain Example 2 of the present invention (0.27 g, 20%), which was an orange solid.

[0548] Synthesis Comparison Example 2

[0549]

[0550] Add 2,6-dimethylpyridine (129.7 mg, 140 μL, 1 equivalent, 1.211 mmol) to a suspension of 12 (1.000 g, 1 equivalent, 1.211 mmol) and 1-(3,5-diisopropyl-[1,1'-biphenyl]-4-yl)-2-(phenanthro[3,2-b]benzofuran-11-yl)-1H-benzo[d]imidazole 11 (751.6 mg, 1 equivalent, 1.211 mmol) in 2-ethoxyethanol (20 mL). Heat the mixture to 122 °C for 64 hours. Remove the resulting mixture from the heat and allow it to cool to room temperature. Purify the crude product by silica gel chromatography using elution with 70% toluene in heptane. Combine the eluates containing the product and concentrate under reduced pressure. The solid was dried in a vacuum oven at 50°C for 3 hours to obtain Comparative Example 2 (1.12 g, 75%), which was a yellow solid.

[0551] Calculation results

[0552]

[0553] Calculations were also performed using examples and comparative examples of the present invention. Referring to the first structure described above, example 1 of the present invention has R. 1 =CD3, R 2 =TMS, R 3 and R 4 =Isopropyl structure, while Comparative Example 1 has R 1 =CD3, R 2 =H,R 3 and R 4 =Isopropyl structure. Referring to the second structure above, Example 2 of the present invention has an R... 1 =adamantyl, R 2 =H,R 3 and R 4 =Isopropyl structure, while Comparative Example 2 has R 1 = tert-butyl, R 2 =H,R 3 and R 4 =The structure of isopropyl. Van der Waals surface area R 1 (VdW), R 2 (VdW), R 3 (VdW) and R 4 (VdW), R 1 (VdW)+R 3 (VdW), R 1 (VdW)+R 4 (VdW), R 2(VdW)+R 3 (VdW) and R 2 (VdW)+R 4 The sum of (VdW) and the cone angle R 1 (CA), R 2 (CA), R 3 (CA) and R 4 The calculation results of (CA) are shown below.

[0554] Table 1

[0555]

[0556]

[0557] Device Examples

[0558] Through high vacuum (<10) -7 The apparatus for manufacturing all examples of thermal evaporation is described. The anode electrode is... Indium tin oxide (ITO). The cathode is made of... Liq (8-hydroxyquinoline lithium), and subsequently The device is composed of Al. All devices were immediately sealed in a nitrogen glove box (H2O and O2 < 1 ppm) with an epoxy-sealed glass lid, incorporating a desiccant into the packaging. The organic stack of the device examples, starting from the ITO surface, consists of the following sequence: HATCN serves as a hole injection layer (HIL); HTM serves as the hole transport layer (HTL); EBM serves as an electron blocking layer (EBL); its thickness is... The emission layer (EML); containing H body (H1):E body (H2) in a ratio of 7:3 and 5% by weight of green emitter; H2 is used as a hole blocking layer (HBL); and it is doped with 35% ETM. Liq (lithium 8-hydroxyquinoline) was used as the ETL. The device structure is shown in Table 2. The chemical structures of the device materials are also shown below.

[0559]

[0560]

[0561] Table 2. Materials and Thickness of Device Layers

[0562]

[0563] After fabrication, the device was tested to measure electroluminescence (EL) and current density-voltage-luminance (JVL). For this purpose, the sample was tested using a 2-channel Keysight B2902A SMU at 10 mA / cm². 2 The current density was used for energy determination and measured using a Photo Research PR735 spectroradiometer. Radiometric intensity (W / str / cm²) was collected from 380 nm to 1080 nm. 2 (And total integrated photon count.) The device was then placed under a large-area silicon photodiode for JVL scanning. The device was used at 10 mA / cm². 2 The integrated photon counting method converts the photodiode current into a photon count. The scanning voltage is 0 to 200 mA / cm². 2 The voltage. The EQE of each device was calculated using the total integrated photon count. All results are summarized in Tables 3 and 4 below. The LE and EQE of Example 1 (Device 1) are reported as relative numbers normalized relative to the results of Comparative Example 1 (Device 2). The LE and EQE of Example 2 (Device 3) are reported as relative numbers normalized relative to the results of Comparative Example 2 (Device 4).

[0564] Table 3. Results of the apparatus

[0565]

[0566] Table 4. Results of the apparatus

[0567]

[0568] Tables 3 and 4 provide a performance overview of several electroluminescent devices. Compared to Comparative Example 1 (FWHM = 60 nm), Example 1 of the present invention (device 1) exhibits a narrower lineshape with an FWHM of 57 nm. Similarly, compared to Comparative Example 2 (FWHM = 29 nm), Example 2 of the present invention (device 3) exhibits a narrower lineshape with an FWHM of 28 nm. Generally, phosphorescent emitter complexes have a wider FWHM. Achieving a narrow FWHM value has always been a goal. The narrower the FWHM, the better the color purity for display applications. As background information, the ideal lineshape is a single wavelength (single line). As can be seen here, due to the features of the present invention, the compounds of the present invention can reduce the FWHM value relative to the comparative compounds. The TMS group on Example 1 of the present invention and the adamantyl group on Example 2 of the present invention have large cone angles and van der Waals surfaces. Although not wishing to be bound by theory, it is believed that those features bring the TMS and adamantyl group close to one of the isopropyl groups on the emitting ligand to rigidify the entire molecule, thereby producing a narrow spectrum in the device. Furthermore, compared to the LE and EQE values ​​of Comparative Example 2, Example 2 of the present invention produces higher LE and EQE values. These improvements exceed any values ​​attributable to experimental error, and the observed improvements are significant. The performance improvements observed in the above data are unexpected. All results demonstrate the significance of applying the compounds of the present invention to organic light-emitting diodes (OLEDs).

Claims

1. A compound of formula Ir(L A ) x (L B ) y of formula I: wherein: each of x and y is independently 1 or 2, and x+y = 3; X 1 to X 17 each of X is independently C or N; R A , R B , R C , R D , and R E each independently represent mono-substitution to the maximum allowable substitution or no substitution; each R 1 , R 2 , R 3 , R 4 , R A , R B , R C , R D , and R E are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfido, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof; any two substituents can be joined or fused to form a ring; R 1 , R 2 , R 3 , or R 4 is not hydrogen, deuterium, or halogen; R 1 , R 2 , R 3 , and R 4 each have a corresponding cone angle R 1 (CA), R 2 (CA), R 3 (CA), and R 4 (CA); each of R 1 , R 2 , R 3 , and R 4 has a corresponding van der Waals surface area R 1 (VdW), R 2 (VdW), R 3 (VdW), and R 4 (VdW); and at least one of the following is true: (i) and R 1 (CA) or R 3 at least one of (CA) is > target cone angle, (ii) and R 1 (CA) or R 4 (CA) is at least the target cone angle, (iii) and R 2 (CA) or at least one of R 3 (CA) is ≥ the target cone angle, or (iv) and R 2 (CA) or R 4 (CA) is at least the target cone angle; wherein the target cone angle is 35 degrees.

2. The compound of claim 1, wherein each of X 1 to X 17 is C, or wherein at least one of X 1 to X 17 is N; and / or wherein the first ligand L A comprises an electron- withdrawing group selected from the group consisting of the list of EWG1 defined herein; and / or wherein at least one of R 1 , R 2 , R 3 , or R 4 comprises a tertiary alkyl group; and / or wherein at least one of R 1 , R 2 , R 3 , or R 4 comprises a polycyclic non-aromatic ring system; and / or wherein at least one of R 1 , R 2 , R 3 , and R 4 is a polycyclic spiro ring system; and / or wherein at least one of R 1 , R 2 , R 3 , or R 4 comprises a silyl or germyl group containing at least 4 carbon atoms; and / or the compound comprises a structure of Formula II, wherein: X 18 to X 21 each of X is independently C or N; Y 1 is 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, CRR', SiRR', and GeRR'; R D' represents mono-substitution to the maximum allowable substitution or no substitution; each R D' R and R' are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfido, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof; and any two substituents can be joined or fused to form a ring.

3. The compound of claim 1, wherein R 1 and R 2 are different; and / or wherein R 3 and R 4 are the same; and / or wherein at least one of R 1 , R 2 , R 3 , or R 4 is selected from the group consisting of the structures in List 1 below:

4. The compound of claim 1, wherein two R A are joined or fused to form a cyclic moiety A1, wherein moiety A1 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; and / or wherein two R B are joined or fused to form a cyclic moiety B1, wherein moiety B1 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; and / or wherein two R C are joined or fused to form a cyclic moiety C1, wherein moiety C1 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring; and / or wherein two R D are joined or fused to form a cyclic moiety D1, wherein moiety D1 is a monocyclic or polycyclic fused ring system, wherein each ring in the monocyclic or polycyclic fused ring system is independently a 5- to 10-membered carbocyclic or heterocyclic ring.

5. The compound of claim 1, wherein at least one R A comprising a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or wherein at least one R B comprising a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or wherein at least one R C comprising a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or wherein at least one R D comprising a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or wherein at least one R E comprising a substituent selected from the group consisting of alkyl, cycloalkyl, silyl, germyl, aryl, heteroaryl, and combinations thereof; and / or wherein the ligand L A is selected from the group consisting of the structures in List 2 below: wherein: X1to X 23 each of X1to X4is independently C or N; each of Y1and Y2is independently 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, CRR', SiRR', and GeRR'; R D1 and each of R D2 independently represents mono-substitution to the maximum allowable substitution or no substitution; each R, R', R D1 and R D2 is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfido, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof; and any two substituents can be joined or fused to form a ring.

6. The compound according to claim 1, wherein the ligand L A selected from the list of Ligands 3 defined in the following consisting of: wherein: Y A and each of Y B is independently selected from the group consisting of BR, BR', NR, PR, P(O)R, O, S, Se, C=O, C=S, C=Se, C=NR', C=CRR', S=O, SO2, CRR', SiRR', and GeRR'; R CC , R DD , R DD1 , R DD2 , and R EE each independently represents mono-substitution to the maximum allowable substitution or no substitution; each R, R', R CC , R DD , R DD1 , R DD2 , and R EE is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfido, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof; the remaining variables are the same as previously defined; and any two substituents can be joined or fused to form a ring.

7. The compound of claim 1, wherein the ligand L A is selected from L Ai (Rm)(Rn)(Ro)(Rp)(Rq)(Rr), wherein i is an integer from 1 to 38, Rm is selected from R131 to R250, Rn is selected from R1 to R250, each of Ro, Rp, Rq, and Rr is independently selected from R1 to R130, and L A1 (R131)(R1)(R1)(R1)(R1)(R1) to L A38 (R250)(R250)(R130)(R130)(R130)(R130) are each defined in List 4 below: or wherein the ligand L A selected from L A'i' (Rm')(Rn)(Ro)(Rp)(Rq)(Rr), wherein i' is an integer from 1 to 38, Rm' is selected from R1 to R250, and L A'1 (R1)(R1)(R1)(R1)(R1)(R1) to L A'38 Each of (R250)(R250)(R130)(R130)(R130)(R130) is defined in the following List 5: wherein R1to R130have the structures defined in List 6 as defined herein; and wherein R131to R250have the structures defined in List 1 as defined herein.

8. The compound of claim 1, wherein Ligand L B is selected from the group consisting of the structures in List 7: wherein: R AA and each of R BB independently represents mono-substitution to the maximum allowable substitution or no substitution; each R AA and R BB is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfido, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof; the remaining variables are the same as previously defined; and any two substituents can be joined or fused to form a ring.

9. The compound according to claim 1, wherein the ligand L B is selected from L Bk wherein k is an integer from 1 to 541, and L B1 to L B541 Each of L 10. The compound of claim 1, wherein the ligand L B is selected from L B'k' (Ri)(Rj)(Rk)(Rl), wherein k' is an integer from 1 to 35, wherein Ri is selected from the group consisting of R131 to R250, each of Rj, Rk, and Rl is independently selected from the group consisting of R1 to R250, and L B'k' each of (Ri)(Rj)(Rk)(Rl) is defined in the following List 9: wherein R1to R130have the structures defined in List 6 below: and wherein R131to R250have the structures defined in List 1 as defined herein.

11. The compound of claim 7, wherein L A is selected from L Ai (Rm)(Rn)(Ro)(Rp)(Rq)(Rr) or L A'i' (Rm')(Rn)(Ro)(Rp)(Rq)(Rr), wherein i is an integer from 1 to 38; i' is an integer from 1 to 38; and L B is selected from L Bk or L B'k' (Ri)(Rj)(Rk)(Rl), wherein k is an integer from 1 to 541, k' is an integer from 1 to 35, wherein: when the compound is of formula Ir(L Ai (Rm)(Rn)(Ro)(Rp)(Rq)(Rr))(L Bk )2, the compound is selected from the group consisting of Ir(L A1 (R131)(R1)(R1)(R1)(R1)(R1))(L B1 )2 to Ir(L A38 (R250)(R250)(R130)(R130)(R130)(R130))(L B541 )2consisting of when the compound is of formula Ir(L Ai (Rm)(Rn)(Ro)(Rp)(Rq)(Rr))(L B'k' (Ri)(Rj)(Rk)(Rl))2, the compound is selected from the group consisting of Ir(L A1 (R131)(R1)(R1)(R1)(R1)(R1))(L B'1 (R131)(R1)(R1)(R1))2 to Ir(L A38 (R250)(R250)(R130)(R130)(R130)(R130))(L B'35 (R250)(R250)(R250)(R250))2consisting of when the compound is of formula Ir(L A'i' (Rm')(Rn)(Ro)(Rp)(Rq)(Rr))(L B'k' (Ri)(Rj)(Rk)(Rl))2, the compound is selected from the group consisting of Ir(L A1 (R1)(R1)(R1)(R1)(R1)(R1))(L B'1 (R131)(R1)(R1)(R1))2 to Ir(L A'38 (R250)(R250)(R130)(R130)(R130)(R130))(L B'35 (R250)(R250)(R250)(R250))2 consisting of; when the compound is of formula Ir(L Ai (Rm)(Rn)(Ro)(Rp)(Rq)(Rr))2(L Bk ), the compound is selected from the group consisting of Ir(L A1 (R131)(R1)(R1)(R1)(R1)(R1))2(L B1 ) to Ir(L A38 (R250)(R250)(R130)(R130)(R130)(R130))2(L B541 )consisting of when the compound is of formula Ir(L Ai (Rm)(Rn)(Ro)(Rp)(Rq)(Rr))2(L B'k' (Ri)(Rj)(Rk)(Rl)) is selected from the group consisting of Ir(L A1 (R131)(R1)(R1)(R1)(R1)(R1))2(L B'1 (R131)(R1)(R1)(R1)) to Ir(L A38 (R250)(R250)(R130)(R130)(R130)(R130))2(L B'35 (R250)(R250)(R250)(R250)) consisting of when the compound is of formula Ir(L A'i' (Rm')(Rn)(Ro)(Rp)(Rq)(Rr))2(L B'k' (Ri)(Rj)(Rk)(Rl)) is selected from the group consisting of Ir(L A1 (R1)(R1)(R1)(R1)(R1)(R1))2(L B'1 (R131)(R1)(R1)(R1)) to Ir(L A'38 (R250)(R250)(R130)(R130)(R130)(R130))2(L B'35 (R250)(R250)(R250)(R250)) consisting of the group.

12. The compound of claim 1, wherein the compound is selected from the group consisting of the structures in List 10 below:

13. An organic light emitting device (OLED) comprising: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound according to claim 1.

14. The OLED of claim 13, wherein the organic layer further comprises a host, wherein the host is selected from the group consisting of the following host Group 1: wherein: each of J1to J6is independently C or N; L' is a direct bond or an organic linking group; 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, BRR'; R A' , R B' , R C' , R D' , R E' , R F' , and R G' each independently represent mono-substitution, up to maximum 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 the generic substituents as defined herein; any two substituents can be joined or fused to form a ring; and where possible, each unsubstituted aromatic carbon atom is optionally replaced with one or more N to form a nitrogen substituted ring.

15. A consumer product comprising an organic light emitting device (OLED), the OLED comprising: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound according to claim 1.

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