CN117186157A

CN117186157A - Organic electroluminescent material and device

Info

Publication number: CN117186157A
Application number: CN202310677090.7A
Authority: CN
Inventors: 辛卫春; 亚力克西·鲍里索维奇·迪亚特金; 皮埃尔·吕克·T·布德罗; 林春; 姬志强; 陈小凡; R·哈姆泽; T·费利塔姆
Original assignee: Universal Display Corp
Current assignee: Universal Display Corp
Priority date: 2022-06-08
Filing date: 2023-06-08
Publication date: 2023-12-08

Abstract

The present application relates to organic electroluminescent materials and devices. Providing a formula IIs a first ligand L of (2) _A Is a compound of (a). In formula I, moieties a and B are each a single ring or multiple ring fused ring system; z is Z ¹ To Z ⁴ Each is C or N; k is a direct bond, O or S; each R ^A And R is ^B Independently hydrogen or a generic substituent; at least one R ^A Or R is ^B R is of the formula II- - - -L-GeR ¹ R ² R ³ A structure; l is a direct bond or an organic linking group; and L is _A Coordination to metal M by dashed lines; and the metal M is selected from Ir, rh, re, ru, os, pt, pd, ag, au or Cu.

Description

Organic electroluminescent material and device

Cross reference to related applications

The present application is U.S. patent application Ser. No. 17/959,324 filed on even date 4 of 10/2022 herein; U.S. patent application Ser. No. 18/058,461, filed 11/23 at 2022; U.S. patent application Ser. No. 18/297,699, filed on 10/4/2023; U.S. patent application Ser. No. 18/297,759, filed on 10/4/2023; U.S. patent application Ser. No. 18/297,781, filed 4/10/2023; U.S. patent application Ser. No. 18/297,693, filed on 10/4/2023; U.S. patent application Ser. No. 18/297,752, filed on 10/4/2023; and U.S. patent application Ser. No. 17/743,561, filed on 5/13 of 2022, the entire contents of all of which are hereby incorporated by reference. The present application is based on U.S. c. ≡119 (e) claim 2023, U.S. provisional application No. 63/501,049 filed on 5/9; U.S. provisional application No. 63/391,173, filed on 7/21 of 2022; U.S. provisional application No. 63/350,150 filed on 8/6/2022; U.S. provisional application No. 63/351,049 filed on 6/10 of 2022; U.S. provisional application No. 63/354,721, filed on 6/23 at 2022; U.S. provisional application No. 63/406,019 filed on day 13 9 of 2022; U.S. provisional application No. 63/407,981, filed on 9/19 of 2022; U.S. provisional application No. 63/417,746 filed on day 10 and 20 of 2022; U.S. provisional application No. 63/481,143, filed on day 23 of month 1 of 2023; U.S. provisional application No. 63/392,731, filed on 7.2022; and U.S. provisional application No. 63/385,730, filed on 1 at 12 at 2022, the entire contents of all of which are incorporated herein by reference.

Technical Field

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

Background

Optoelectronic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many of the materials used to fabricate the devices are relatively inexpensive, so organic photovoltaic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials (e.g., their flexibility) may make them more suitable for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials.

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

One application of phosphorescent emissive molecules is in full color displays. Industry standards for such displays require pixels adapted to emit a particular color (referred to as a "saturated" color). In particular, these standards require saturated red, green and blue pixels. Alternatively, the OLED may be designed to emit white light. In conventional liquid crystal displays, the emission from a white backlight is filtered using an absorbing filter to produce red, green and blue emissions. The same technique can also be used for OLEDs. The white OLED may be a single emissive layer (EML) device or a stacked structure. The colors may be measured using CIE coordinates well known in the art.

Disclosure of Invention

Novel Pt-and Ir-organometallic complexes having ligands containing Ge atoms are provided that are suitable for use as phosphorescent emitters in OLEDs.

In one aspect, the present disclosure provides a composition of formula I,is a first ligand L of (2) _A Is a compound of (a). In formula I:

moieties a and B are each independently a monocyclic 5-or 6-membered carbocycle or heterocycle or a polycyclic fused ring system comprising at least two rings, wherein each of said at least two rings is independently a 5-or 6-membered carbocycle or heterocycle;

Z ¹ to Z ⁴ Each independently is C or N;

k is a direct bond, O or S;

R ^A and R is ^B Each independently represents mono-substitution to the maximum allowable substitution or no substitution;

each R ^A And R is ^B Independently hydrogen or selected fromSubstituents of the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof;

at least one R ^A Or R is ^B R is of the formula II- - - -L-GeR ¹ R ² R ³ A structure;

L is a direct bond or an organic linking group;

each R ¹ 、R ² And R is ³ Independently selected from the group consisting of: alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;

L _A coordination to metal M by dashed lines;

the metal M is selected from the group consisting of: ir, rh, re, ru, os, pt, pd, ag, au and Cu;

L _A can be conjugated with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands;

any two substituents may be joined or fused to form a ring.

In another aspect, the present disclosure provides a formulation comprising a first ligand L as described herein having formula I _A Is a compound of (a).

In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a first ligand L as described herein having formula I _A Is a compound of (a).

In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a first ligand L having formula I as described herein _A Is a compound of (a).

Drawings

Fig. 1 shows an organic light emitting device.

Fig. 2 shows an inverted organic light emitting device without a separate electron transport layer.

Detailed Description

A. Terminology

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

as used herein, the term "organic" includes polymeric materials and small molecule organic materials that can be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and may be substantial in nature. In some cases, the small molecule may include a repeating unit. For example, the use of long chain alkyl groups as substituents does not remove a molecule from the "small molecule" class. Small molecules may also be incorporated into the polymer, for example as pendant groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core of a dendrimer, which consists of a series of chemical shells built on the core. The core moiety of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. Dendrimers may be "small molecules" and all dendrimers currently used in the OLED field are considered small molecules.

As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed" over "a second layer, the first layer is disposed farther from the substrate. Unless a first layer is "in contact with" a second layer, other layers may be present between the first and second layers. For example, a cathode may be described as "disposed over" an anode even though various organic layers are present between the cathode and the anode.

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

A ligand may be referred to as "photosensitive" when it is believed that the ligand contributes directly to the photosensitive properties of the emissive material. When the ligand is considered not to contribute to the photosensitive properties of the emissive material, the ligand may be referred to as "ancillary", but the ancillary ligand may alter the properties of the photosensitive ligand.

As used herein, and as will be generally understood by those of skill in the art, if the first energy level is closer to the vacuum energy level, then the first "highest occupied molecular orbital" (Highest Occupied Molecular Orbital, HOMO) or "lowest unoccupied molecular orbital" (Lowest Unoccupied Molecular Orbital, LUMO) energy level is "greater than" or "higher than" the second HOMO or LUMO energy level. Since 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). Similarly, a higher LUMO energy level corresponds to an Electron Affinity (EA) with a smaller absolute value (less negative EA). On a conventional energy level diagram with vacuum energy level on top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. The "higher" HOMO or LUMO energy level appears closer to the top of this figure than the "lower" HOMO or LUMO energy level.

As used herein, and as will be generally understood by those of skill in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Since work function is typically measured as a negative number relative to the vacuum level, this means that the "higher" work function is more negative (more negative). On a conventional energy level diagram with the vacuum energy level on top, a "higher" work function is illustrated as being farther from the vacuum energy level in a downward direction. Thus, the definition of HOMO and LUMO energy levels follows a different rule than work function.

The terms "halo", "halogen" and "halo" are used interchangeably and refer to fluoro, chloro, bromo and iodo.

The term "acyl" refers to a substituted carbonyl (C (O) -R _s )。

The term "ester" refers to a substituted oxycarbonyl (-O-C (O) -R) _s or-C (O) -O-R _s ) A group.

The term "ether" means-OR _s A group.

The terms "thio" or "thioether" are used interchangeably and refer to-SR _s A group.

The term "selenoalkyl" refers to-SeR _s A group.

The term "sulfinyl" refers to-S (O) -R _s A group.

The term "sulfonyl" refers to-SO ₂ -R _s A group.

The term "phosphino" refers to-P (R _s ) ₃ A group wherein each R _s May be the same or different.

The term "silane group" means-Si (R _s ) ₃ A group wherein each R _s May be the same or different.

The term "germyl" refers to-Ge (R _s ) ₃ A group wherein each R _s May be the same or different.

The term "borane" refers to-B (R _s ) ₂ A group or Lewis addition product-B (R) _s ) ₃ A group, wherein R is _s May be the same or different.

In each of the above, R _s May be hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R _s Selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

The term "alkyl" refers to and includes straight and branched chain alkyl groups. Preferred alkyl groups are those containing from one to fifteen carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, and the like. In addition, alkyl groups may be optionally substituted.

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

The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, si and Se, preferably O, S or N. In addition, heteroalkyl or heterocycloalkyl groups may be optionally substituted.

The term "alkenyl" refers to and includes both straight and branched alkenyl groups. Alkenyl is essentially an alkyl group comprising at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl is essentially cycloalkyl including at least one carbon-carbon double bond in the cycloalkyl ring. The term "heteroalkenyl" as used herein refers to an alkenyl group having at least one carbon atom replaced with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, si and Se, preferably O, S or N. Preferred alkenyl, cycloalkenyl or heteroalkenyl groups are those containing from two to fifteen carbon atoms. In addition, alkenyl, cycloalkenyl, or heteroalkenyl groups may be optionally substituted.

The term "alkynyl" refers to and includes both straight and branched chain alkynyl groups. Alkynyl is essentially an alkyl group that includes at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing from two to fifteen carbon atoms. In addition, alkynyl groups may be optionally substituted.

The term "aralkyl" or "arylalkyl" is used interchangeably and refers to an alkyl group substituted with an aryl group. In addition, aralkyl groups may be optionally substituted.

The term "heterocyclyl" 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, N, P, B, si and Se, preferably O, S or N. Aromatic heterocyclic groups may be used interchangeably with heteroaryl. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl, and the like, and cyclic ethers/sulfides such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. In addition, the heterocyclic group may be optionally substituted.

The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groupsAnd polycyclic aromatic ring systems. The polycyclic ring may have two or more rings in common in which two carbons are two adjoining rings (the rings being "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. Preferred aryl groups are those containing from six to thirty carbon atoms, preferably from six to twenty carbon atoms, more preferably from six to twelve carbon atoms. Particularly preferred are aryl groups having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, triphenylene, fluorene and naphthalene. In addition, aryl groups may be optionally substituted.

The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. Heteroatoms include, but are not limited to O, S, N, P, B, si and Se. In many cases O, S or N are preferred heteroatoms. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have one to six heteroatoms. The heteropolycyclic ring system may have two or more rings in which two atoms are common to two adjoining rings (the rings being "fused"), wherein at least one of the rings is heteroaryl, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. The heteropolycyclic aromatic ring system may have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from three to thirty carbon atoms, preferably from three to twenty carbon atoms, more preferably from three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, diazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene (xanthene), acridine, phenazine, phenothiazine, phenoxazine, benzofurandipyridine, benzothiophene pyridine, thienodipyridine, benzoselenophene dipyridine, dibenzofuran, dibenzoselenium, carbazole, indolocarbazole, benzimidazole, triazine, 1, 2-borazine, 1-boron-nitrogen, 1-nitrogen, 4-boron-nitrogen, boron-nitrogen-like compounds, and the like. In addition, heteroaryl groups may be optionally substituted.

Of the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and their respective corresponding aza analogues, are of particular interest.

The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclyl, aryl, and heteroaryl as used herein are independently unsubstituted or independently substituted with one or more common substituents.

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

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

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

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

The terms "substituted" and "substituted" refer to substituents other than H bonded to the relevant position, such as carbon or nitrogen. For example, when R ¹ When single substitution is represented, then one R ¹ It must not be H (i.e., substitution). Similarly, when R ¹ When two are substituted, two R ¹ It must not be H. Similarly, when R ¹ R represents zero or no substitution ¹ For example, it may be hydrogen of available valence of the ring atoms, such as carbon atoms of benzene and nitrogen atoms in pyrrole, or for ring atoms having a fully saturated valence, it may simply represent none, such as nitrogen atoms in pyridine. The maximum number of substitutions possible in the ring structure will depend on the total number of available valences in the ring atom.

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 one of ordinary skill in the art can contemplate from the applicable list. For example, alkyl and deuterium can combine to form a partially or fully deuterated alkyl group; halogen and alkyl may combine to form a haloalkyl substituent; and halogen, alkyl and aryl may combine to form a haloaralkyl. In one example, the term substitution includes a combination of two to four of the listed groups. In another example, the term substitution includes a combination of two to three groups. In yet another example, the term substitution includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms other than hydrogen or deuterium, or combinations comprising up to forty atoms other than hydrogen or deuterium, or combinations comprising up to thirty atoms other than hydrogen or deuterium. In many cases, a preferred combination of substituents will include up to twenty atoms that are not hydrogen or deuterium.

The term "aza" in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the C-H groups in the corresponding aromatic ring may be replaced by a nitrogen atom, for example and without limitation, aza-triphenylene encompasses dibenzo [ f, H ] quinoxaline and dibenzo [ f, H ] quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by those of ordinary skill in the art, and all such analogs are intended to be encompassed by the terms as set forth herein.

As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. patent No. 8,557,400, patent publication No. WO 2006/095951, and U.S. patent application publication No. US 2011/0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Yan Ming (Ming Yan) et al, tetrahedron 2015,71,1425-30 and Azrote (Atzrodt) et al, germany application chemistry (Angew. Chem. Int. Ed.) (reviewed) 2007,46,7744-65, which is incorporated by reference in its entirety, describes the deuteration of methylene hydrogen in benzylamine and the efficient pathway of replacement of aromatic ring hydrogen with deuterium, respectively.

It will be appreciated that when a fragment of a molecule is described as a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or linking fragments are considered equivalent.

In some cases, a pair of adjacent substituents may optionally be joined or fused into a ring. Preferred rings are five-, six-, or seven-membered carbocycles or heterocycles, including both cases where a portion of the ring formed by the pair of substituents is saturated and a portion of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that the two substituents involved may be located next to each other on the same ring, or on two adjacent rings having two nearest available substitutable positions (e.g., the 2, 2' positions in biphenyl or the 1, 8 positions in naphthalene) so long as they can form a stable fused ring system.

B. Compounds of the present disclosure

In one aspect, the present disclosure provides a composition of formula I,or formula Ia>Is a first ligand L of (2) _A Is a compound of (a). In formula I and formula Ia:

L ^Z is a direct bond or an organic linking group;

Z ¹ to Z ⁴ Each independently is C or N;

k is a direct bond, O or S;

each R ^A And R is ^B Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein;

l is a direct bond or an organic linking group;

L _A coordination to metal M by dashed lines;

L _A can be combined with other ligands to form threeA tooth, tetradentate, pentadentate or hexadentate ligand; and is also provided with

Any two substituents may be joined or fused to form a ring.

In some embodiments, each of the following conditions is true:

(i) When M is Ir, L is a direct bond, part A is a non-condensed pyridine, Z ² Is N, part B is a non-condensed phenyl group, K is a direct bond, and at least one R ^B When R, then the compound is compounded and does not comprise an acetylacetonate ligand or derivative thereof;

(ii) When M is Ir, A is a non-condensed pyridine, Z ² Is N, part B is a non-condensed phenyl group, K is a direct bond, and at least one R ^A R, then L comprises at least one cyclic group;

(iii) When M is Ir, K is a direct bond, L is a direct bond, part B is a non-condensed naphthalene, and at least one R ^B In the case of R, then the compound does not comprise an acetylacetonate ligand or a derivative thereof;

(iv) When M is Ir, L is a direct bond, Z ² Is N, and at least one R ^A When R is, then Z ² Not a non-fused pyridine ring or a part of a fused pyridine ring, with all other fused rings being phenyl rings;

(v) When M is Ir, L is a direct bond, Z ² Is N and is part of a pyridine ring which is part of a polycyclic fused ring system of part A, and at least one R ^A For R attached to the pyridine ring, then the polycyclic fused ring system of part a comprises at least one five membered ring;

(vi) When M is Pt then L ^A Is a tetradentate ligand and Ge in R does not belong to any ring atom; and is also provided with

(vii) When M is Pt, L is a direct bond, moiety A is a non-fused pyridine, Z ² Is N, and at least one R ^A R, then in addition to moiety B, moiety a is bonded to another fused or non-fused aromatic ring, and the other fused or non-fused aromatic ring is coordinated to Pt; and

(viii) One or more combinations of (i) through (vii).

As used herein, examples of derivatives of acetylacetonate ligands are derivatives wherein the methyl group is replaced by another substituent (a general substituent as defined herein or a preferred general substituent). In some embodiments, each of the methyl groups is independently replaced with a group selected from the group consisting of: alkyl, cycloalkyl, partially or fully deuterated variants thereof, or combinations thereof.

In some embodiments, no more than 10% of the spin density of any of the anions, cations, or lowest excited triplet states is concentrated at R ¹ 、R ² 、R ³ And L. In some embodiments, no more than 5% of the spin density of any of the anions, cations, or lowest excited triplet states is concentrated at R ¹ 、R ² 、R ³ And L. In some embodiments, no more than 1% of the spin density of any of the anions, cations, or lowest excited triplet states is concentrated at R ¹ 、R ² 、R ³ And L.

In some embodiments, no more than 10% of the spin density of any of the anions, cations, or lowest excited triplet states is concentrated in all R ¹ 、R ² 、R ³ And L. In some embodiments, no more than 5% of the spin density of any of the anions, cations, or lowest excited triplet states is concentrated in all R ¹ 、R ² 、R ³ And L. In some embodiments, no more than 1% of the spin density of any of the anions, cations, or lowest excited triplet states is concentrated in all R ¹ 、R ² 、R ³ And L.

In some embodiments, one of the rings in part a or part B is ring Q, R is bonded to ring Q, and no more than 10% of the spin density of any of the anionic, cationic, or lowest excited triplet states is concentrated on ring Q. In some embodiments, one of the rings in part a or part B is ring Q, R is bonded to ring Q, and no more than 5% of the spin density of any of the anionic, cationic, or lowest excited triplet states is concentrated on ring Q. In some embodiments, one of the rings in part a or part B is ring Q, R is bonded to ring Q, and no more than 1% of the spin density of any of the anionic, cationic, or lowest excited triplet states is concentrated on ring Q.

In some embodiments, the shortest number of atoms between a Ge atom in R and an atom having a spin density of greater than 1% of any of the anions, cations, or lowest excited triplet states is at least 2 atoms. In some embodiments, the shortest number of atoms between a Ge atom in R and an atom having a spin density of greater than 1% of any of the anions, cations, or lowest excited triplet states is at least 3 atoms. In some embodiments, the shortest number of atoms between a Ge atom in R and an atom having a spin density of greater than 1% of any of the anions, cations, or lowest excited triplet states is at least 4 atoms. In some embodiments, the shortest number of atoms between a Ge atom in R and an atom having a spin density of greater than 1% of any of the anions, cations, or lowest excited triplet states is at least 5 atoms.

The anion, cation and triplet spin densities of the compounds were calculated using Density Functional Theory (DFT). The calculation was performed using the unrestricted B3LYP functional and CEP-31G basis set. By setting the spin-multiple to three, the first triplet excited state is geometrically optimized in vacuum. Geometric optimization of the first cation and anion bimodality was performed in vacuum by setting the charge to +1 or-1 respectively and the spin-multiplicity to 2. The cube gen utility in the Gaussian (Gaussian) program was then used to calculate spin density as the difference between the alpha and beta spin densities. All calculations were performed using a gaussian program. To determine the number of spin density population per atom and per atomic group, the spin density was measured Population analysis, e.g.>P. -o.chem physical journal (j.chem.Phys.) 1950,18,365 and +.>Advances in Quantum chemistry (Adv Quantum Chem) 1970,5,185. This is achieved by dividing the spin density into disjoint atom-centric specific gravities that together constitute a molecule. These specific gravities are then collected individually or in groups as desired.

In some embodiments, M is Ir, L is a direct bond, moiety A is a non-fused pyridine, Z ² Is N, part B is non-condensed phenyl, K is a direct bond, at least one R ^B Is R and the compound comprises at least one L ^B Which is a phenylpyridine ligand having a silane substituent on the pyridine ring. In some such embodiments, the silane is Si (CH ₃ ) ₃ Or Si (C) ₆ H ₅ ) ₃ 。

In some embodiments, M is Ir, A is a non-fused pyridine, Z ² Is N, B is a non-condensed phenyl group, K is a direct bond, at least one R ^A R and L comprises at least one linking group selected from the group consisting of aryl, heteroaryl, and cycloalkyl. In some embodiments, L comprises cycloalkyl. In some embodiments, L comprises an aryl group. In some embodiments, L comprises phenyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, imidazolyl, pyrazolyl, pyrrolyl, oxazolyl, furanyl, thiophenyl, or thiazolyl. In some embodiments, L comprises a cyclohexyl, cyclopentyl, or fluorenyl group.

With respect to condition (vi), the term "ring atom" includes atoms that are part of the backbone of any ring, including rings comprising metal M (e.g., metallized rings).

In some embodiments, M is Ir, L is a direct bond, Z ² Is N, at least one R ^A Is R and Z ² Not a non-fused pyridine ring or a part of a fused pyridine ring, with all other fused rings being phenyl rings; in some such embodiments, Z is included ² Is fused to a 5-membered ring or a 6-membered heterocyclic ring. In some embodiments, include Z ² Is fused to a ring selected from the group consisting of: pyridine, pyrimidine, pyridazine, pyrazine and triOxazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene and thiazole.

In some embodiments, L ^Z Is a direct bond. In some embodiments, L ^Z 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, SO ₂ CR, CRR ', siRR' and GeRR ', wherein each R and R' is independently selected from the group consisting of preferred general substituents as defined herein. It should be understood that when L ^Z In the case of a direct bond, formula Ia is the same as formula I and all embodiments applicable to formula I should be applicable to formula Ia.

In some embodiments, each R ^A And R is ^B Independently selected from the group consisting of preferred general substituents as defined herein. In some embodiments, each R ^A And R is ^B Independently selected from the group consisting of the more preferred general substituents defined herein. In some embodiments, each R ^A And R is ^B Independently selected from the group consisting of the most preferred general substituents defined herein.

In some embodiments, Z ¹ 、Z ³ And Z ⁴ Each of which is C, and Z ² Is N.

In some embodiments, K is a direct bond. In some embodiments, K is O. In some embodiments, K is S.

In some embodiments, moiety a is a non-fused single ring. In some embodiments, part a is selected from the group consisting of: phenyl, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole.

In some embodiments, moiety a is a non-fused pyridine.

In some embodiments, moiety a is not a non-fused pyridine. In some embodiments, moiety a is a polycyclic fused ring system. In some embodiments, part a is selected from the group consisting of: naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthrene, phenanthridine, and fluorene.

In some embodiments where part A is not a non-fused pyridine ring, Z ² Is N and is part of a pyridine ring.

In some embodiments where part A is not a non-fused pyridine ring, Z ² Is N but is not part of a pyridine ring.

In some embodiments, part B is a single ring. In some embodiments, moiety B is a non-aromatic ring. In some embodiments, moiety B is a cycloalkyl ring. In some embodiments, part B is selected from the group consisting of: cyclopentane, cyclohexane and cycloheptane.

In some embodiments, part B is selected from the group consisting of: phenyl, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole.

In some embodiments, moiety B is a non-fused phenyl group.

In some embodiments, part B is selected from the group consisting of: cyclopentane, cyclohexane, cycloheptane, and fluorene.

In some embodiments, moiety B is a polycyclic fused ring system. In some embodiments, part B is selected from the group consisting of: naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthrine, and phenanthridine.

In some embodiments, part B is not naphthalene.

In some embodiments, two R ^A Joined to form a loop. In some embodiments, two R's are used ^A The ring formed is a 5-or 6-membered carbocyclic or heterocyclic ring. In some embodiments, two R's are used ^A The ring formed is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole.

In some embodiments of the present invention, in some embodiments,two R ^B Joined to form a loop. In some embodiments, two R's are used ^B The ring formed is a 5-or 6-membered carbocyclic or heterocyclic ring. In some embodiments, two R's are used ^B The ring formed is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole.

In some embodiments, each of moieties a and B may independently be a polycyclic fused ring structure. In some embodiments, each of part a and part B may independently be a polycyclic fused ring structure comprising at least three fused rings. In some embodiments, the polycyclic fused ring structure has two 6 membered rings and one 5 membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to metal M and the second 6-membered ring is fused to the 5-membered ring. In some embodiments, each of part a and part B may be independently selected from the group consisting of: dibenzofuran, dibenzothiophene, dibenzoselenophene, and aza variants thereof. In some such embodiments, each of moieties a and B may be further substituted at the ortho or meta position of the O, S or Se atom with a substituent selected from the group consisting of: deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the aza variant contains exactly one N atom at the 6 position (O, S or ortho to Se) and a substituent at the 7 position (O, S or meta to Se).

In some embodiments, each of part a and part B may independently be a polycyclic fused ring structure comprising at least four fused rings. In some embodiments, the polycyclic fused ring structure comprises three 6 membered rings and one 5 membered ring. In some such embodiments, the 5-membered ring is fused to a ring coordinated to the metal M, the second 6-membered ring is fused to the 5-membered ring, and the third 6-membered ring is fused to the second 6-membered ring. In some such embodiments, the third 6-membered ring is further substituted with a substituent selected from the group consisting of: deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

In some embodiments, each of part a and part B may independently be a polycyclic fused ring structure comprising at least five fused rings. In some embodiments, the polycyclic fused ring structure comprises four 6-membered rings and one 5-membered ring or three 6-membered rings and two 5-membered rings. In some embodiments comprising two 5-membered rings, the 5-membered rings are fused together. In some embodiments comprising two 5-membered rings, the 5-membered rings are separated by at least one 6-membered ring. In some embodiments having one 5-membered ring, the 5-membered ring is fused to a ring coordinated to metal M, the second 6-membered ring is fused to the 5-membered ring, the third 6-membered ring is fused to the second 6-membered ring, and the fourth 6-membered ring is fused to the third 6-membered ring.

In some embodiments, each of moieties a and B can independently be an aza form of the polycyclic fused ring described above. In some embodiments, each of moieties a and B may independently contain exactly one aza N atom. In some embodiments, each of moieties a and B may contain exactly two aza N atoms, which may be in one ring or in two different rings. In some embodiments, the ring with the aza N atom is separated from the metal M atom by at least two other rings. In some embodiments, the ring with the aza N atom is separated from the metal M atom by at least three other rings. In some embodiments, each of the ortho positions to the aza N atom is substituted.

In some embodiments, ge in R does not belong to any ring atom.

In some embodiments, at least one R ^A R is. In some embodiments, moiety A is a polycyclic fused ring system and is bonded to a ring system comprising Z ² At least one R of the ring of (2) ^A R is. In some such embodiments, the polycyclic fused ring system of part a comprises at least one ring selected from the group consisting of: imidazole, pyrazole, pyrrole, oxazole, furan, thiophene and thiazole.

In some embodiments, moiety A is a polycyclic fused ring system and is bonded to a ring system other than Z ² At least one R of the ring of (2) ^A R is.

In some embodiments, at least one R ^B R is. In some embodiments, moiety B is a polycyclic fused ring system and is bonded to a ring system comprising Z ⁴ At least one R of the ring of (2) ^B R is. In some embodimentsIn which part B is a polycyclic fused ring system and is bonded to a member other than Z ⁴ At least one R of the ring of (2) ^B R is.

In some embodiments, R ¹ 、R ² And R is ³ Independently an alkyl group, which may be partially or fully deuterated, partially or fully fluorinated. In some such embodiments, R ¹ 、R ² And R is ³ Independently selected from the group consisting of: methyl, ethyl, propyl, isopropyl, n-butyl and tert-butyl.

In some embodiments, R ¹ 、R ² And R is ³ Independently an aryl group, which may be partially or fully deuterated, partially or fully fluorinated. In some embodiments, R ¹ 、R ² And R is ³ Independently phenyl, which may be partially or fully deuterated, partially or fully fluorinated.

In some embodiments, R ¹ 、R ² And R is ³ None of which is bonded or fused to another substituent. In some embodiments, R ¹ 、R ² And R is ³ Joined to form a loop. In some embodiments, L is a direct bond.

In some embodiments, L 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=cr ' R ", s= O, SO ₂ CR, CRR ', siRR ', geRR ', alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof; and each R and R' is independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein.

In some embodiments, L comprises aryl or heteroaryl. In some embodiments, L is aryl. In some embodiments, L is selected from the group consisting of: phenyl, biphenyl, terphenyl, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthridine, and fluorene, which may be further substituted.

In some embodiments, L is phenyl or biphenyl, which may be further substituted with a substituent selected from the group consisting of the general substituents defined herein.

In some of the above embodiments, any substituent of L may be joined or fused to form a ring with its adjacent substituents. In some embodiments, the substituents of L may be in combination with R ¹ 、R ² And R is ³ Joined or fused to form a ring.

In some embodiments, ge in R is directly attached to moiety a or B.

In some embodiments, ge in R is not directly attached to moiety a or B.

In some embodiments, ge in R belongs to a ring atom of the first ring.

In some embodiments, ge in R belongs to a ring atom of the first ring fused to moiety a or B.

In some embodiments, ge in R belongs to a ring atom of a first ring fused to one or more rings prior to being fused to moiety a or B.

In some embodiments, ge in R belongs to a ring atom of the first ring fused to one or more rings but not fused to moieties a or B.

In some embodiments, the metal M is Ir. In some embodiments, the metal M is Pt or Pd.

In some embodiments, moiety B is not a monocyclic (e.g., non-fused) phenyl group. In some embodiments, L ^A Is a tetradentate ligand. In some embodiments, R ¹ 、R ² Or R is ³ None of them is equal to R ^A Or R is ^B Joined to form a loop.

In some embodiments, ligand L _A Selected from the group consisting of the structures of the following list 1:

/>

wherein:

X ¹ -X ¹² each independently is C or N;

each of Z and Z' is 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, SO ₂ CR, CRR ', siRR ', and GeRR ';

R ^AA 、R ^BB and R is ^CC Independently represents a single substitution up to the maximum number of substitutions or no substitutions possible;

each R, R', R ^AA 、R ^BB And R is ^CC Independently hydrogen or a substituent selected from the group consisting of general substituents; and is also provided with

Any two substituents may be joined or fused to form a ring.

In some embodiments, ligand L _A Selected from the group consisting of the structures of the following list 2:

/>

wherein:

z 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, SO ₂ CR, CRR ', siRR ', and GeRR ';

R ^AA and R is ^BB Independently represents a single substitution up to the maximum number of substitutions or no substitutions possible;

each R, R', R ^AA And R is ^BB Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with

Any two substituents may be joined or fused to form a ring.

In some embodiments, geR ¹ R ² R ³ The group may be GeMe ₃ 、GeEt ₃ 、Ge( ⁱ Pr) ₃ 、Ge( ^t Bu) ₃ 、GePh ₃ 、Ge(CD ₃ ) ₃ 、CH ₂ GeMe ₃ 、CD ₂ GeMe ₃ 、GeMeEt ₂ 、GeMe( ⁱ Pr) ₂ 、GeMe( ^t Bu) ₂ 、

In some embodimentsIn GeR ¹ R ² R ³ The groups may be/>

In some embodiments, ligand L _A Selected from the group consisting of: l (L) _A 1-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ ) To L _A 2-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ )、L _A 3-(R ^A1 )(R ^A2 )(R ^B1 )(R ^B2 )(L')(R ¹ )(R ² )(R ³ ) To L _A 4-(R ^A1 )(R ^A2 )(R ^B1 )(R ^B2 )(L')(R ¹ )(R ² )(R ³ )、L _A -(R ^A1 )(R ^A2 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ ) To L _A 10-(R ^A1 )(R ^A2 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ )、L _A 11-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ ) To L _A 12-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ )、L _A 13-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(R ^B2 )(L)(R ¹ )(R ² )(R ³ ) To L _A 20-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(R ^B2 )(L)(R ¹ )(R ² )(R ³ )、L _A 21-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ ) To L _A 28-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ )、L _A 29-(R ^A1 )(R ^A2 )(R ^B1 )(R ^B2 )(L)(R ¹ )(R ² )(R ³ ) To L _A30 -(R ^A1 )(R ^A2 )(R ^B1 )(R ^B2 )(L)(R ¹ )(R ² )(R ³ )、L _A 31-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(R ^B2 )(L)(R ¹ )(R ² )(R ³ ) To L _A 38-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(R ^B2 )(L)(R ¹ )(R ² )(R ³ )、L _A 39-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ ) To L _A 42-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(R ^B2 )(L)(R ¹ )(R ² )(R ³ )、L _A 43-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(R ^B2 )(L)(R ¹ )(R ² )(R ³ ) To L _A 44-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(R ^B2 )(L)(R ¹ )(R ² )(R ³ )、L _A 45-(R ^A1 )(R ^A2 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ ) To L _A 100-(R ^A1 )(R ^A2 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ )、L _A 101-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ ) To L _A 118-(R ^A1 )(R ^A2 )(R ^A3 )(R ^B1 )(L)(R ¹ )(R ² )(R ³ ) Wherein R is ^A1 、R ^A2 、R ^A3 、R ^B1 、R ^B2 、R ¹ 、R ² And R is ³ Each of which is independently selected from structures R1 to R80, L is selected from structures L1 to L10, and L' is selected from structures L1 to L8, and wherein L _A 1- (R1) (R1) (R1) (R1) (L1) (R1) (R1) to L _A 118- (R80) (L10) (R80) each has a structure defined in the following list 3:

/>

wherein R1 to R80 have the structure defined in the following list 4: />

wherein L1 to L10 have the structure defined in the following list 5:/>

wherein the dotted line labeled # is bonded to either part a or part B.

In some embodiments, the compound has the formula M (L _A ) _p (L _B ) _q (L _C ) _r Wherein L is _B And L _C Each being a bidentate ligand; and wherein p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; and p+q+r is the oxidation state of the metal M.

In some embodiments, the compound has a formula selected from the group consisting of: ir (L) _A ) ₃ 、Ir(L _A )(L _B ) ₂ 、Ir(L _A ) ₂ (L _B )、Ir(L _A ) ₂ (L _C ) And Ir (L) _A )(L _B )(L _C ) The method comprises the steps of carrying out a first treatment on the surface of the And wherein L is _A 、L _B And L _C Different from each other.

In some embodiments, L _B Is a substituted or unsubstituted phenylpyridine, and L _C Is a substituted or unsubstituted acetylacetonate.

In some embodiments, the compound may have the formula Pt (L _A )(L _B ) The method comprises the steps of carrying out a first treatment on the surface of the And wherein L is _A And L _B May be the same or different. In such embodiments, L _A And L is equal to _B To form a tetradentate ligand.

In some embodiments, L _B And L _C Each independently selected from the group consisting of the structures of the following list 6:

/>

t is selected from the group consisting of B, al, ga and In;

wherein K is ¹ ' is a direct bond or is selected from the group consisting of: NR (NR) _e 、PR _e O, S and Se;

wherein each Y ¹ To Y ¹³ Independently selected from the group consisting of carbon and nitrogen;

wherein Y' is selected from the group consisting of: BR (BR) _e 、NR _e 、PR _e 、O、S、Se、C＝O、S＝O、SO ₂ 、CR _e R _f 、SiR _e R _f And GeR _e R _f ；

R _e And R is _f Can be fused or joined to form a ring;

wherein each R is _a 、R _b 、R _c And R is _d May independently represent a single to the maximum number of possible substitutions or no substitution;

wherein each R is _a1 、R _b1 、R _c1 、R _d1 、R _a 、R _b 、R _c 、R _d 、R _e And R is _f Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with

Wherein R is _a1 、R _b1 、R _c1 、R _d1 、R _a 、R _b 、R _c And R is _d Any two of which may be fused or joined to form a ring or to form a multidentate ligand.

In some such embodiments, L _B And L _C Neither is equal to

In some embodiments, L _B And L _C Each independently selected from the group consisting of the structures of the following list 7:

in some embodiments, L _B And L _C Each independently selected from the group consisting of the structures of the following list 8:

/>

wherein:

R _a '、R _b '、R _c '、R _d ' and R _e ' each independently represents zero substitution, a single substitution, or up to a maximum allowable number of substitutions to its associated ring;

R _a1 、R _b1 、R _c1 、R _a 、R _b 、R _c 、R _N 、R _a '、R _b '、R _c '、R _d ' and R _e Each of' is independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with

Any two R _a1 、R _b1 、R _c1 、R _a 、R _b 、R _c 、R _N 、R _a '、R _b '、R _c '、R _d ' and R _e ' may be fused or joined to form a ring or to form a multidentate ligand.

In some such embodiments, L _B And L _C Neither is equal to

In some embodiments, L _B And L _C Each independently selected from the group consisting of the structures of the following list 8 a:

/>

in some embodiments, the compound may have the formula Ir (L _A ) ₃ Ir (L) _A )(L _Bk ) ₂ Ir (L) _A ) ₂ (L _Bk ) Ir (L) _A ) ₂ (L _Cj-I ) Ir (L) _A ) ₂ (L _Cj-II ) Ir (L) _A )(L _Bk )(L _Cj-I ) Or Ir (L) _A )(L _Bk )(L _Cj-II ) Wherein L is _A Is a ligand as defined herein for formula I; l (L) _Bk As defined herein; and L is _Cj-I And L _Cj-II Each as defined herein.

In some embodiments, the compound has the formula Ir (L _A ) ₃ Ir (L) _A )(L _Bk ) ₂ Ir (L) _A ) ₂ (L _Bk ) Ir (L) _A ) ₂ (L _Cj-I ) Or Ir (L) _A ) ₂ (L _Cj-II )，

Wherein L is _A Can be any L described herein _A ；

Wherein k is an integer from 1 to 520;

wherein each L _Bk Having the structure defined in the following list 9:

/>

wherein each L _Cj-I Has a structure based on the following formula:and is also provided with

Each L _Cj-II Has a structure based on the following formula:wherein for L _Cj-I And L _Cj-II Each L of (3) _Cj ，R ²⁰¹ And R is ²⁰² Each independently defined in the following list 10:

/>

wherein R is ^D1 To R ^D246 Has the structure shown in the following list 11:

/>

In some embodiments, the compound is selected from the group consisting of only L thereof _Bk A group consisting of those compounds corresponding to one of: l (L) _B1 、L _B2 、L _B18 、L _B28 、L _B38 、L _B108 、L _B118 、L _B122 、L _B124 、L _B126 、L _B128 、L _B130 、L _B132 、L _B134 、L _B136 、L _B138 、L _B140 、L _B142 、L _B144 、L _B156 、L _B158 、L _B160 、L _B162 、L _B164 、L _B168 、L _B172 、L _B175 、L _B204 、L _B206 、L _B214 、L _B216 、L _B218 、L _B220 、L _B222 、L _B231 、L _B233 、L _B235 、L _B237 、L _B240 、L _B242 、L _B244 、L _B246 、L _B248 、L _B250 、L _B252 、L _B254 、L _B256 、L _B258 、L _B260 、L _B262 、L _B264 、L _B265 、L _B266 、L _B267 、L _B268 、L _B269 And L _B270 。

In some embodiments, the compound is selected from the group consisting of only L thereof _Bk A group consisting of those compounds corresponding to one of: l (L) _B1 、L _B2 、L _B18 、L _B28 、L _B38 、L _B108 、L _B118 、L _B122 、L _B126 、L _B128 、L _B132 、L _B136 、L _B138 、L _B142 、L _B156 、L _B162 、L _B204 、L _B206 、L _B214 、L _B216 、L _B218 、L _B220 、L _B231 、L _B233 、L _B237 、L _B264 、L _B265 、L _B266 、L _B267 、L _B268 、L _B269 And L _B270 。

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

In some embodiments, the compounds are selected from only those having L _Cj-I Or L _Cj-II A group consisting of compounds of ligands whose corresponding R ²⁰¹ And R is ²⁰² Is defined as one selected from the following structures: r is R ^D1 、R ^D3 、R ^D4 、R ^D5 、R ^D9 、R ^D10 、R ^D17 、R ^D22 、R ^D43 、R ^D50 、R ^D78 、R ^D116 、R ^D118 、R ^D133 、R ^D134 、R ^D135 、R ^D136 、R ^D143 、R ^D144 、R ^D145 、R ^D146 、R ^D149 、R ^D151 、R ^D154 、R ^D155 R ^D190 、R ^D193 、R ^D200 、R ^D201 、R ^D206 、R ^D210 、R ^D214 、R ^D215 、R ^D216 、R ^D218 、R ^D219 、R ^D220 、R ^D227 、R ^D237 、R ^D241 、R ^D242 、R ^D245 And R is ^D246 。

In some embodiments, the compounds are selected from those directed to L only _Cj-I A compound of which the ligand has one of the following structures:

/>

in some embodiments, the first ligand L comprising formula I _A The compound of (a) may be selected from the group consisting of:

/>

wherein:

X ⁹⁶ to X ⁹⁹ Is independently C or N;

each Y ¹⁰⁰ Independently selected from the group consisting of NR ", O, S and Se;

R ^10a 、R ^20a 、R ^30a 、R ^40a and R is ^50a Independently represents a single substitution up to a maximum substitution or no substitution;

R、R'、R”、R ^10a 、R ^11a 、R ^12a 、R ^13a 、R ^20a 、R ^30a 、R ^40a 、R ^50a 、R ⁶⁰ 、R ⁷⁰ 、R ⁹⁷ 、R ⁹⁸ and R is ⁹⁹ Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein;

R ^10a 、R ^20a 、R ^30a 、R ^40a Or R is ^50a At least one of them has the formula II, -L-GeR ¹ R ² R ³ Is of a structure of (2); and is also provided with

Any two 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 is ⁹⁹ May be joined or fused to form a ring.

In some embodiments, the compound is selected from the group consisting of the structures of the following list 12:

/>

in some embodiments, the compound has the structure of formula III:

wherein:

M ¹ pd or Pt;

moieties E and F are each independently a single or multiple ring structure comprising 5-and/or 6-membered carbocycles or heterocycles;

Z ⁵ and Z ⁶ Each independently is C or N;

K ¹ and K ² Each independently selected from the group consisting of a direct bond, O and S, wherein the K ¹ And K ² At least two of which are direct bonds;

L ¹ 、L ² and L ³ Each independently selected from the group consisting of: direct bond, BR, BRR ', NR, PR, P (O) R, O, S, se, C = O, C = S, C =se, c=nr, c=crr', s= O, SO ₂ CR, CRR ', siRR ', geRR ', alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof, wherein L ¹ And L ² In (a) and (b)At least one present;

R ^E and R is ^F Each independently represents zero substitution, a single substitution, or up to a maximum allowable number of substitutions to its associated ring;

R、R'、R ^E and R is ^F Independently hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein; and is also provided with

Where chemically feasible, any two R, R', R ^A 、R ^B 、R ^C 、R ^E And R is ^F May be joined or fused together to form a ring.

In some embodiments of formula III, both moieties E and F are 6 membered aromatic rings.

In some embodiments of formula III, moiety F is a 5-or 6-membered heteroaromatic ring.

In some embodiments of formula III, L ¹ Is O or CRR'.

In some embodiments of formula III, Z ⁶ Is N and Z ⁵ Is C. In some embodiments of formula III, Z ⁶ Is C and Z ⁵ Is N.

In some embodiments of formula III, L ² Is a direct bond. In some embodiments of formula III, L ² Is NR.

In some embodiments of formula III, K, K ¹ And K ² Are direct bonds. In some embodiments of formula II, K, K ¹ And K ² One of them is O.

In some embodiments of formula III, the compound is selected from the group consisting of:

/>

wherein:

l is independently selected from the group consisting of: direct bond, BR "R '", NR ", PR", O, S, se, C = O, C = S, C =se, c=nr ", c=cr" R' ", s= O, SO ₂ CR ", CR" R ' ", siR" R ' ", ger" R ' ", alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

X ¹⁰⁰ At each occurrence selected from the group consisting of: o, S, se, NR "and CR" R' ";

each R ^A ”、R ^B ”、R ^C ”、R ^D ”、R ^E "and R ^F "independently means monosubstituted, up to maximum substituted or unsubstituted;

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 which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, borane, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereofCombining; and 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 At least one of "comprises a germyl group.

In some embodiments, the compound may have formula IV;

ring E is a 5-or 6-membered carbocyclic or heterocyclic ring;

Q ¹ to Q ¹⁵ Is C or N;

Each R ^A ”、R ^B ”、R ^C ”、R ^D ”、R ^E "and R ^F "independently means monosubstituted, up to most substituted or unsubstituted;

R”、R”'、R ^A ”、R ^B ”、R ^C ”、R ^D ”、R ^E ”、R ^F ”、R ^S1 and R is ^S2 Each of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, borane, aralkyl, alkoxy, aryloxy, amino, silyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof; and R ', R', R ^A1 '、R ^A2 '、R ^A ”、R ^B ”、R ^C ”、R ^D ”、R ^E ”、R ^F ”、R ^S1 And R is ^S2 Comprises a germyl group;

where chemically feasible, any two R ", R'", R ^A ”、R ^B ”、R ^C ”、R ^D ”、R ^E ”、R ^F ”、R ^S1 And R is ^S2 May be joined or fused together to form a ring.

In some embodiments, at least one of the following eleven conditions is true;

1.R ^S1 comprises a germyl group.

2.R ^S1 And R is ^S2 Different.

3.R ^S1 And R is ^S2 Each comprising a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, borane, aralkyl, alkoxy, aryloxy, amino, silyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof.

4.Q ¹ To Q ¹⁵ At least one of which is N.

5. Ring E is a heterocycle.

6.Q ¹² Is C and R ^D" To be at Q ¹² A non-hydrogen substituent substituted at the moiety.

7.R ^S1 And R is ^S2 At least one of which is a substituted phenyl ring.

8. At least one R ^D" Is a substituted phenyl ring.

9.L is selected from the group consisting of: BR ", BR" R '", PR", NR ", S, se, c= O, C = S, C =se, c=nr", c=cr "R'", s= O, SO ₂ CR ", CR" R ' ", siR" R ' ", ger" R ' ", alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

10.R”、R”'、R ^A ”、R ^B ”、R ^C ”、R ^D ”、R ^E ”、R ^F ”、R ^S1 And R is ^S2 At least two of which are joined or fused together to form a ring, provided that if two R' s ^F "join to form a benzene ring, then R", R' ", R ^A ”、R ^B ”、R ^C ”、R ^D ”、R ^E ”、R ^F ”、R ^S1 And R is ^S2 At least two other of which are joined or fused together to form a ring.

11.1 to 10.

In some embodiments, R ^S1 And R is ^S2 At least one of which is together with R ^F "join to form a ring.

In some embodiments, two R ^F "joined to form a 5 to 12 membered ring.

In some embodiments, two R ^F "join to form a 6 membered ring.

In some embodiments, R ^S1 And R is ^S2 Each is a 5-or 6-membered ring, substituted or unsubstituted.

In some embodiments, R ^S1 And R is ^S2 Each is a substituted or unsubstituted phenyl ring.

In some embodiments, R ^S1 And R is ^S2 Each independently is a substituted phenyl ring.

In some embodiments, R ^S1 And R is ^S2 Each a phenyl ring substituted with a substituent selected from the group consisting of: deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, silyl, germyl, aryl, heteroaryl, nitrile, and combinations thereof.

In some embodiments, R ^S1 And R is ^S2 At least one of which is an alkyl group.

In some embodiments, R ^S1 And R is ^S2 Is selected from the group consisting of fully or partially deuterated alkyl groups, fully or partially deuterated cycloalkyl groups, fully or partially deuterated aryl groups, silane groups, tertiary butyl groups, and combinations thereof.

In some embodiments, Q ¹² Is C and is selected from the group consisting of deuterium, alkyl, aryl, silane, germanyl, and combinations thereofR of the group ^D "substitution".

In some embodiments, ring E is an imidazole ring.

In some embodiments, two R ^E "join to form a ring.

In some embodiments of formula III, the compound is selected from the group consisting of the structures of the following list 13:

/>

wherein R is ^AA 、R ^BB 、R ^DD 、R ^EE And R is ^FF Each independently represents a single substitution to the maximum allowable fetchSubstituted or unsubstituted;

X ₁ 、X ₂ 、X ₃ 、X ₄ 、X ₅ 、X ₆ 、X ₇ and X ₈ Each independently is C or N;

each R ^N 、R ^AA 、R ^BB 、R ^DD 、R ^EE And R is ^FF Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with

Any two substituents may be joined or fused to form a ring.

In some embodiments, the compound is selected from the group consisting of the compounds defined in the following list 14:

/>

wherein each of o, p, q, r, s, t, u and v is independently an integer from 1 to 86; and w is an integer from 1 to 10; and is also provided with

Wherein R is ¹ To R ⁸⁶ Having the structure defined in the following list 15:

/>

and wherein T1 to T10 have the structure defined in the following list 16:

/>

wherein:

R ^A ”、R ^B ”、R ^C ”、R ^D ”、R ^E "and R ^F "each independently means monosubstituted to maximally substituted or unsubstituted;

Each 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 is ^N" Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein;

R ^A ”、R ^B ”、R ^C ”、R ^D ”、R ^E "or R ^F At least one of "has the formula II, - - -L-GeR ¹ R ² R ³ Is of a structure of (2); and is also provided with

Any two 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 "optionally joined to form a ring".

In some embodiments of formula III, moiety a is bonded to another fused or non-fused aromatic ring in addition to moiety B, and the other fused or non-fused aromatic ring coordinates to Pt.

In some embodiments, the compound is selected from the group consisting of: />

wherein at least one R ^D" R is; or (b)

At least one of themR ^C" R is; or (b)

Wherein at least one R ^A" R is; or (b)

Wherein at least one R ^E" R is.

In some embodiments, the compound is selected from the group consisting of the structures of the following list 16:

/>

in another aspect, the present disclosure provides a compound having the structure of formula IIIA:

wherein:

M ¹ pd or Pt;

moieties A, B, E and F are each independently a single or multiple ring structure comprising a 5-and/or 6-membered carbocyclic or heterocyclic ring;

Z ¹ to Z ⁸ Each independently is C or N;

K、K ¹ 、K ² and K ³ Each independently selected from the group consisting of a direct bond, O and S, wherein the K, K ¹ 、K ² And K ³ At least two of which are direct bonds;

each of m and n is 0 or 1; when m is 0, L ¹ Absence of; when m is 1, L ¹ Presence; when n is 0, L ³ Absence of; when n is 1, L ³ Presence; m+n is at least 1;

each L ¹ 、L ² 、L ³ And L ⁴ Independently selected from the group consisting of: direct bond, BR, BRR ', NR, PR, P (O) R, O, S, se, C = O, C = S, C =se, c=nr, c=crr', s= O, SO ₂ CR, CRR ', siRR ', geRR ', alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof;

each R ^A 、R ^B 、R ^E And R is ^F Independently represents zero substitution, single substitution or up to a maximum allowable number of substitutions for its associated ring;

R、R'、R ^A 、R ^B 、R ^E and R is ^F Each of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof;

at least one R ^A 、R ^B 、R ^E And R is ^F Comprises R, wherein R is of formula II, -L-GeR ¹ R ² R ³ Is of a structure of (2);

l is a direct bond or an organic linking group;

each R ¹ 、R ² And R is ³ Independently selected fromThe group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof;

where chemically feasible, any two R' s ¹ 、R ² 、R ³ 、R、R'、R ^A 、R ^B 、R ^E And R is ^F May be joined or fused together to form a ring.

In some embodiments, each of the following conditions is true:

(1) When M is Pt and Ge in R belongs to a ring atom of the first ring, then the remaining ring atoms and ring bonds of the first ring do not contain any L ¹ 、L ² 、L ³ And L ⁴ ；

(2) When M is Pt, M is 1, n is 0, L ⁴ Is a direct bond, L ² For direct bond or c=crr', Z ² And Z ⁶ Is N, Z ⁴ And Z ⁵ When C is then L ¹ Is not NR; and is also provided with

(3) When M is Pt, Z ² Is N, at least one R ^A When R is, then part a is not a non-fused pyrazole.

In some embodiments, the compound comprises at least one metal-carbene bond.

In some embodiments, the compound comprises at least one metal-O bond.

In some embodiments, each K, K ¹ 、K ² And K ³ Is a direct bond.

In some embodiments, K is O, each K ¹ 、K ² And K ³ Is a direct bond.

In some embodiments, Z ² 、Z ⁴ 、Z ⁵ And Z ⁶ Two of which are C and Z ² 、Z ⁴ 、Z ⁵ And Z ⁶ And two of them are N.

In some embodiments, three of Z2, Z4, Z5, and Z6 are C, and the remaining one of Z2, Z4, Z5, and Z6 is N.

In some embodiments, m+n is 1. In some embodiments, m=0, and n=1. In some embodiments, m=1 and n=0. In some embodiments, L ⁴ Is a direct bond.

In some embodiments, three of the moieties A, B, E and F are each independently a 6 membered carbocyclic or heterocyclic ring, and the remaining one of the moieties A, B, E and F is a 5 membered heterocyclic ring.

In some embodiments, each of moieties A, B, E and F is independently a 6-membered carbocyclic or heterocyclic ring.

In some embodiments, each moiety of A, B, E and F is independently a non-fused 5-or 6-membered carbocyclic or heterocyclic ring.

In some embodiments, at least one of moieties A, B, E and F is a fused 5-or 6-membered carbocyclic or heterocyclic ring.

In some embodiments, at least two of moieties A, B, E and F are fused 5-or 6-membered carbocycles or heterocycles.

In some embodiments, each of portions A, B, E and F is independently selected from the group consisting of: phenyl, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and heterocyclic carbene.

In some embodiments, each of portions A, B, E and F is independently selected from the group consisting of: phenyl, pyridine, pyrimidine, imidazole, furan, thiophene, and imidazole-derived carbenes.

In some embodiments, R, R', R ^A 、R ^B 、R ^E And R is ^F Each of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, borane, and combinations thereof; and wherein each R ¹ 、R ² And R is ³ Independently selected from the group consisting of: alkyl, heteroalkyl, cycloalkyl, heterocycloalkylAryl, heteroaryl, and combinations thereof.

In some embodiments, each L ¹ 、L ² 、L ³ And L ⁴ Independently selected from the group consisting of direct bond, NR, c=crr', and O.

In some embodiments, ge in R is directly attached to moiety A, B, E or F.

In some embodiments, ge in R is not directly attached to moiety A, B, E or F.

In some embodiments, ge in R belongs to a ring atom of the first ring.

In some embodiments, ge in R belongs to a ring atom of the first ring fused to moiety A, B, E or F.

In some embodiments, ge in R belongs to a ring atom of a first ring fused to one or more rings prior to being fused to moiety A, B, E or F.

In some embodiments, ge in R belongs to a ring atom of the first ring fused to one or more rings but not fused to moiety A, B, E or F.

In some embodiments, ge in R is comprised of one of the following structures selected from the group consisting of:

wherein each R is ^1w To R ^14w Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof; and wherein any two R ^1w To R ^14w May be joined or fused into a ring.

In some embodiments, R ^1w To R ^14w To form a bridged fused ring system. In some embodiments, at least one pair of adjacent R's attached to the same atom ^1w To R ^14w Joined to form a helical structure. In some embodiments, at least one R ^1w To R ^14w Partially or fully deuterated, partially or fully fluorinated, or a combination thereof.

In some embodiments, the compound of formula IIIA has a structure derived from R ^A And R is ^B A first substituent R of one of ^I Which is at R ^I Has the structure shown in R ^A And R is ^B All atoms in (1) are at medium distance M ¹ A first atom furthest away; from R ^E And R is ^F A second substituent R of one of ^II Which is at R ^II Has the structure shown in R ^E And R is ^F All atoms in (1) are at medium distance M ¹ A first atom furthest away; wherein:

distance D ¹ Is R ^I M in (v) ¹ A distance to the first atom;

distance D ² Is R ^II M in (v) ¹ A distance to the first atom;

define a sphere with radius r centered at M ¹ And radius R is such that it will allow the sphere to encompass a compound in which it is not a substituent R ^I And R is ^II A minimum radius of all atoms of a portion of (a); and is also provided with

Wherein D is ¹ And D ² Is at least longer than r

In some embodiments, D ¹ And D ² Is at least longer than rIn some embodiments, D ¹ And D ² At least +.r longer than r>In some embodiments, D ¹ And D ² At least +.r longer than r>In some embodiments, D ¹ And D ² At least +.r longer than r>In some embodiments, D ¹ And D ² At least +.r longer than r>In some embodiments, D ¹ And D ² At least +.r longer than r>In some embodiments, D ¹ And D ² At least +.r longer than r>In some embodiments, D ¹ And D ² Is at least longer than rIn some embodiments, D ¹ And D ² At least +.r longer than r>In some embodiments, D ¹ And D ² At least +.r longer than r>In some embodiments, D ¹ And D ² At least +.r longer than r>In some embodiments, D ¹ And D ² At least +.r longer than r>

In some embodiments, the compound of formula IIIA has a transition dipole moment axis; and wherein the dipole moment axis is shifted with respect to edge D ¹ Or D ² The angle between the axes of (a) is less than 40. In some embodiments, the compound of formula IIIA has a transition dipole moment axis; and wherein the dipole moment axis is shifted with respect to edge D ¹ Or D ² The angle between the axes of (a) is less than 30. In some embodiments, the compound of formula IIIA has a transition dipole moment axis; and wherein the dipole moment axis is shifted with respect to edge D ¹ Or D ² The angle between the axes is less than 20. In some embodiments, the compound of formula IIIA has a transition dipole moment axis; and wherein the dipole moment axis is shifted with respect to edge D ¹ Or D ² The angle between the axes is less than 15. In some embodiments, the compound of formula IIIA has a transition dipole moment axis; and wherein the dipole moment axis is shifted with respect to edge D ¹ Or D ² The angle between the axes is less than 10.

In some embodiments, the compound of formula IIIA has a vertical dipole ratio; wherein the vertical dipole ratio has a value of 0.33 or less. In some embodiments, the compound of formula IIIA has a vertical dipole ratio; wherein the vertical dipole ratio has a value of 0.30 or less. In some embodiments, the compound of formula IIIA has a vertical dipole ratio; wherein the vertical dipole ratio has a value of 0.25 or less. In some embodiments, the compound of formula IIIA has a vertical dipole ratio; wherein the vertical dipole ratio has a value of 0.20 or less. In some embodiments, the compound of formula IIIA has a vertical dipole ratio; wherein the vertical dipole ratio has a value of 0.15 or less.

In some embodiments, the compound of formula IIIA is selected from the group consisting of the structures of list 13 defined herein;

wherein R is ^AA 、R ^BB 、R ^DD 、R ^EE And R is ^FF Each independently represents mono-substitution to the maximum allowable substitution or no substitution;

each R ^N 、R ^AA 、R ^BB 、R ^DD 、R ^EE And R is ^FF Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof; and is also provided with

Any two substituents may be joined or fused to form a ring.

In some embodiments, the compound of formula IIIA is selected from the group consisting of the compounds defined in list 14 defined herein;

wherein each of o, p, q, r, s, t, u and v is independently an integer from 1 to 86; and is also provided with

Wherein R1 to R86 have the structure defined in list 15 as defined herein.

In some embodiments, the compound of formula IIIA is selected from the group consisting of the structures of list 16 defined herein. In some embodiments, the compound is selected from the group consisting of compounds having the formula Pt (L _A” ) A group consisting of compounds of (Ly'):

wherein L is _A” Selected from the group consisting of the following structures (list 17):

/>

Wherein L is _Y' Selected from the group consisting of the following structures (list 18):

/>

wherein R is ^AA 、R ^BB 、R ^CC 、R ^DD 、R ^EE 、R ^FF 、R ^GG 、R ^HH 、R ^II 、R ^E 、R ^F And R is ^X At least one of them comprises the formula II, -L-GeR ¹ R ² R ³ ；

Wherein Ph represents phenyl;

wherein X is ¹ 、X ² 、X ³ 、X ⁴ 、X ⁵ 、X ⁶ 、X ⁷ 、X ⁸ 、X ⁹ 、X ¹⁰ And X ¹¹ Each independently is C or N;

wherein Y is ^AA Selected from O, S, se, NR, BR or CRR';

wherein each R is ¹ 、R ² 、R ³ 、R ^AA 、R ^BB 、R ^CC 、R ^DD 、R ^EE 、R ^FF 、R ^GG 、R ^HH 、R ^II 、R ^E 、R ^F And R is ^X Independently selected from the group consisting of the structures of the following list 18 a: />

/>

in some embodiments, the compound is selected from the group consisting of compounds having the formula Pt (L _A' ) A group consisting of compounds of (Ly):

wherein L is _A” A structure selected from the following list 19:

/>

and wherein Ly "is the same as the structure in manifest 18.

In some embodiments, the compound is selected from the group consisting of compounds having the formula Pt (L _A” ) A group consisting of compounds of (Ly'):

wherein L is _A' Selected from the group consisting of: l (L) _A” 1-(Ri)(Rj)(Rk)-L _A” 56- (Ri) (Rj) (Rk)); wherein i, j, k, L, m, n, o, p and q are each independently integers from 1 to 135, and wherein L _A” 1- (R1) (R1) (R1) to L _A 56- (R135) are each defined in the following list 20:

/>

wherein L is _y' Selected from the group consisting of the structures in the following list 21:

/>

wherein each of n, u, v, w, x, y, z, q, r, s, b ', c', e ', t', w 'and z' is independently an integer from 1 to 135;

wherein R1 to R135 are defined in the following list 21:

/>

In some embodiments, the compound is selected from the group consisting of:

/>

it should be understood that some of the structural features of the present disclosure are intended to be interchangeable/adaptable throughout the present disclosure, so long as they are chemically feasible. It is also understood that electron withdrawing related groups are applicable to all structures of the present disclosure.

In some embodiments, the compounds described herein 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, deuteration percentage has its ordinary meaning and includes the percentage of possible hydrogen atoms (e.g., hydrogen or deuterium sites) replaced by deuterium atoms.

In some embodiments of the compounds, the compounds comprise at least one electron withdrawing group (R). The electron withdrawing group typically comprises one or more highly electronegative elements including, but not limited to, fluorine, oxygen, sulfur, nitrogen, chlorine, and bromine. In some embodiments of the compounds, the electron withdrawing group has a Hammett constant (Hammett constant) greater than 0. In some embodiments, the Hammett constant of the electron withdrawing group is 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.

In some embodiments, the electron withdrawing group is selected from the group consisting of structures in the following list EWG 1: F. CF (compact flash) ₃ 、CN、COCH ₃ 、CHO、COCF ₃ 、COOMe、COOCF ₃ 、NO ₂ 、SF ₃ 、SiF ₃ 、PF ₄ 、SF ₅ 、OCF ₃ 、SCF ₃ 、SeCF ₃ 、SOCF ₃ 、SeOCF ₃ 、SO ₂ F、SO ₂ CF ₃ 、SeO ₂ CF ₃ 、OSeO ₂ CF ₃ 、OCN、SCN、SeCN、NC、 ⁺ N(R ^k2 ) ₃ 、(R ^k2 ) ₂ CCN、(R ^k2 ) ₂ CCF ₃ 、CNC(CF ₃ ) ₂ 、BR ^k3 R ^k2 Substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1, 9-substituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridoxine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkylAryl groups, partially and fully fluorinated heteroaryl groups, cyano-containing alkyl groups, cyano-containing aryl groups, cyano-containing heteroaryl groups, isocyanates,

Wherein Y is ^G Selected from the group consisting of: BR (BR) _e 、NR _e 、PR _e 、O、S、Se、C＝O、S＝O、SO ₂ 、CR _e R _f 、SiR _e R _f And GeR _e R _f' The method comprises the steps of carrying out a first treatment on the surface of the And is also provided with

R ^k1 Each independently represents mono-substitution to the maximum allowable substitution or no substitution;

Wherein R is ^k1 、R ^k2 、R ^k3 、R _e And R is _f Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein.

In some embodiments, the electron withdrawing group is selected from the group consisting of structures in the following list EWG 2:

/>

in some embodiments, the electron withdrawing group is selected from the group consisting of structures in the following list EWG 3:

/>

in some embodiments, the electron withdrawing group is selected from the group consisting of structures in the following list EWG 4:

in some embodiments, the electron withdrawing group is a pi-electron deficient electron withdrawing group. In some embodiments, the Pi-electron deficient electron withdrawing group is selected from the group consisting of structures in the following list Pi-EWG: CN, COCH ₃ 、CHO、COCF ₃ 、COOMe、COOCF ₃ 、NO ₂ 、SF ₃ 、SiF ₃ 、PF ₄ 、SF ₅ 、OCF ₃ 、SCF ₃ 、SeCF ₃ 、SOCF ₃ 、SeOCF ₃ 、SO ₂ F、SO ₂ CF ₃ 、SeO ₂ CF ₃ 、OSeO ₂ CF ₃ 、OCN、SCN、SeCN、NC、 ⁺ N(R ^k1 ) ₃ 、BR ^k1 R ^k2 Substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1, 9-substituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridazine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,

Wherein all variables are the same as defined above.

In some embodiments of the compounds having ligands of formula I or Ia, R ^A Or R is ^B Is an electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compounds, R ^A Or R is ^B Is an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compounds, R ^A Or R is ^B Is an electron withdrawing group from the list EWG 3 as defined herein. In some embodiments of the compounds, R ^A Or R is ^B Is an electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of the compounds, R ^A Or R is ^B Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments of the compounds having ligands of formula I or Ia, at least one R ^A Is an electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compounds, at least one R ^A Is an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compounds, at least one R ^A Is an electron withdrawing group from the list EWG 3 as defined herein. In some embodiments of the compounds, at least one R ^A Is an electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of the compounds, at least one R ^A Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments of the compounds having ligands of formula I or Ia, at least one R ^B For the absorption from the list EWG 1 as defined hereinAn electron group. In some embodiments of the compounds, at least one R ^B Is an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compounds, at least one R ^B Is an electron withdrawing group from the list EWG 3 as defined herein. In some embodiments of the compounds, at least one R ^B Is an electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of the compounds, at least one R ^B Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments of the compounds having ligands of formula I, the ligands of formula I comprise at least one electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compounds having ligands of formula I, the ligands of formula I comprise at least one electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compounds having ligands of formula I, the ligands of formula I comprise at least one electron withdrawing group from the list EWG 3 as defined herein. In some embodiments of the compounds having ligands of formula I, the ligands of formula I comprise at least one electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of the compounds having ligands of formula I, the ligands of formula I comprise at least one electron withdrawing group from the list Pi-EWG as defined herein.

In some embodiments of the compounds having a ligand of formula Ia, the ligand of formula Ia comprises at least one electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compounds having a ligand of formula Ia, the ligand of formula Ia comprises at least one electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compounds having a ligand of formula Ia, the ligand of formula Ia comprises at least one electron withdrawing group from the list EWG 3 as defined herein. In some embodiments of the compounds having ligands of formula Ia, the ligands of formula Ia comprise at least one electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of compounds having ligands of formula Ia, the ligands of formula Ia comprise at least one electron withdrawing group from the list Pi-EWG as defined herein.

In some embodiments of the compounds of formula III or formula IIIA, R ^A 、R ^B 、R ^E Or R is ^F Is an electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compounds, R ^A 、R ^B 、R ^E Or R is ^F Is an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compounds, R ^A 、R ^B 、R ^E Or R is ^F Is an electron withdrawing group from the list EWG 3 as defined herein. In some embodiments of the compounds, R ^A 、R ^B 、R ^E Or R is ^F Is an electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of the compounds, R ^A 、R ^B 、R ^E Or R is ^F Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments of the compounds of formula III or formula IIIA, one R ^A Is an electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compound, one R ^A Is an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compound, one R ^A Is an electron withdrawing group from the list EWG 3 as defined herein. In some embodiments of the compound, one R ^A Is an electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of the compound, one R ^A Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments of the compounds of formula III or formula IIIA, one R ^B Is an electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compound, one R ^B Is an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compound, one R ^B Is an electron withdrawing group from the list EWG 3 as defined herein. In some cases of compoundsIn one embodiment, one R ^B Is an electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of the compound, one R ^B Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments of the compounds of formula III or formula IIIA, one R ^E Is an electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compound, one R ^E Is an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compound, one R ^E Is an electron withdrawing group from the list EWG 3 as defined herein. In some embodiments of the compound, one R ^E Is an electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of the compound, one R ^E Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments of the compounds of formula III or formula IIIA, one R ^F Is an electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compound, one R ^F Is an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compound, one R ^F Is an electron withdrawing group from the list EWG 3 as defined herein. In some embodiments of the compound, one R ^F Is an electron withdrawing group from the list EWG 4 as defined herein. In some embodiments of the compound, one R ^F Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments of the compounds of formula III or formula IIIA, ligand L _A Comprising an electron withdrawing group from the list EWG 1 as defined herein. In some embodiments of the compounds, ligand L _A Comprising an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compounds, ligand L _A Comprising an electron withdrawing group from the list EWG 3 as defined herein. In some embodiments of the compounds, ligand L _A Comprising an electron withdrawing group from the list EWG 4 as defined herein. In the process of chemical conversionIn some embodiments of the compounds, ligand L _A Comprising electron withdrawing groups from a list Pi-EWG as defined herein.

In some embodiments of the compounds of formula III or formula IIIA, the compound comprises an electron withdrawing group from list EWG 1 as defined herein. In some embodiments of the compounds, the compounds comprise an electron withdrawing group from the list EWG 2 as defined herein. In some embodiments of the compounds, the compounds comprise electron withdrawing groups from the list EWG 3 as defined herein. In some embodiments of the compounds, the compounds comprise electron withdrawing groups from the list EWG 4 as defined herein. In some embodiments of the compounds, the compounds comprise electron withdrawing groups from the list Pi-EWG as defined herein.

In some embodiments, R and R are attached to the same ring. In some embodiments, R and R are attached to different rings but on the same fused ring system. In some embodiments, R and R are attached to different fused ring systems. In some embodiments, R and R are attached to different rings that are not fused to each other. In some embodiments, R and R are attached to the same ligand. In some embodiments, R and R are linked to different ligands.

In some embodiments, the present disclosure provides an Ir (L _A ) _p (L _B ) _q (L _C ) _r A compound, wherein:

first ligand L _A Having the formula I&，A structure; ligand L _B Having the formula II&，/>A structure; and ligand L _C Is a bidentate ligand. In Ir (L) _A ) _p (L _B ) _q (L _C ) _r Among the compounds:

p is 1 or 2; q is 0, 1 or 2; r is 0, 1 or 2;

p+q+r＝3；

moieties a and B are each independently a single ring or a multiple ring fused ring system, wherein each ring in the single ring and the multiple ring fused ring system is independently a 5-or 6-membered carbocycle or heterocycle;

X ¹ to X ⁸ And Z ¹ To Z ⁴ Is independently C or N;

y 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=cr ' R ", s= O, SO ₂ CR, CRR ', siRR ', and GeRR ';

R ^1& 、R ^2& 、R ^3& 、R ^4& and R is ^5& Independently represents a single substitution to the maximum allowable substitution or no substitution;

Each R, R', R ^1& 、R ^2& 、R ^3& 、R ^4& And R is ^5& Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein;

any two R, R', R ^1& 、R ^2& 、R ^3& 、R ^4& Or R is ^5& May be joined or fused to form a ring, or to form a tetradentate or hexadentate ligand;

at least one R ^1& 、R ^2& 、R ^3& 、R ^4& Or R is ^5& Comprises at least one germanyl or silane group; and is also provided with

At least one R ^1& 、R ^2& 、R ^3& 、R ^4& Or R is ^5& Comprising at least one electron withdrawing group.

In some embodiments, at least one R ^1& Comprising an electron withdrawing group.

In some embodiments, the electron withdrawing group is selected from the group consisting of the structures of list EWG1 as defined herein. In some embodiments, the electron withdrawing group is selected from the group consisting of structures of list EWG2 as defined herein. In some embodiments, the electron withdrawing group is selected from the group consisting of the structures of list EWG3 as defined herein. In some embodiments, the electron withdrawing group is selected from the group consisting of structures of list EWG4 as defined herein. In some embodiments, the electron withdrawing group is a Pi-electron deficient electron withdrawing group consisting of the structure of the list Pi-EWG as defined herein.

In some embodiments, the electron withdrawing group may be cyano or as defined herein

In some embodiments, if ring A and ring B are both non-fused pyridine rings, and R ^4& And R is ^5& At least one of which is a germyl group, then (a) X ⁵ To X ⁸ At least one of which is N or (b) Y is other than O.

In some embodiments, if X ⁵ C is then bonded to X ^5& R of (2) ^1& Selected from the group consisting of: hydrogen, deuterium, cycloalkyl, methyl, phenyl, silane, germanyl, and combinations thereof. In some embodiments, if X ⁵ C is then bonded to X ^5& R of (2) ^1& Selected from the group consisting of: H. d, me, ph, substituted or unsubstituted silane groups, substituted or unsubstituted germanyl groups, and partially or fully deuterated variants thereof.

In some embodiments, each R ^1& 、R ^2& 、R ^3& 、R ^4& And R is ^5& Independently hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein. In some embodiments, each R ^1& 、R ^2& 、R ^3& 、R ^4& And R is ^5& Independently hydrogen or a substituent selected from the group consisting of more preferred general substituents as defined herein. In some embodiments, each R ^1& 、R ^2& 、R ^3& 、R ^4& And R is ^5& Independently hydrogen or a substituent selected from the group consisting of the most preferred general substituents defined herein.

In some embodiments, the germyl group is-Ge #R _s ) ₃ Wherein each R is _s Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. In some embodiments, preferably, R _s Selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

In some embodiments, the silane group is-Si (R _s ) ₃ Wherein each R is _s Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. In some embodiments, each R _s Independently selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

In some embodiments, the germyl groups are selected from the group consisting of: geMe ₃ 、GeEt ₃ 、Ge( ⁱ Pr) ₃ 、Ge( ^t Bu) ₃ 、GePh ₃ 、Ge(CD ₃ ) ₃ 、CH ₂ GeMe ₃ 、CD ₂ GeMe ₃ 、GeMeEt ₂ 、GeMe( ⁱ Pr) ₂ 、GeMe( ^t Bu) ₂ 、

In some embodiments, the silane groups are selected from the aforementioned silane group analogs. As used herein, ⁱ pr represents isopropyl and ^t bu represents tert-butyl.

In some embodiments, any two R _s May be joined or fused to form a ring. In some embodiments, the germyl groups are selected from the group consisting of: in some embodiments, the silane groups are selected from silane-based analogs of the foregoing structure, wherein two R _s Joined or fused to form a ring.

In some embodiments, Z ¹ Is C and Z ² Is N. In some embodiments, Z ¹ Is N and Z ² Is C.

In some embodiments, Z ³ Is C and Z ⁴ Is N. In some embodiments, Z ³ Is N and Z ⁴ Is C.

In some embodiments, p is 1. In some embodiments, p is 2.

In some embodiments, X ¹ To X ⁴ Each of which is C.

In some embodiments, X ¹ To X ⁴ At least one of which is N. In some embodiments, X ¹ To X ⁴ Exactly one of (2) is N.

In some embodiments, X ⁵ To X ⁸ Each of which is C.

In some embodiments, X ⁵ To X ⁹ At least one of which is N. In some embodiments, X ⁵ To X ⁹ Exactly one of (2) is N.

In some embodiments, X ⁵ Is N, and X ⁶ To X ⁸ Each of which is C. In some embodiments, X ⁶ Is N, and X ⁵ 、X ⁷ And X ⁸ Each of which is C.

In some embodiments, X ⁷ Is N, and X ⁵ 、X ⁶ And X ⁸ Each of which is C. In some embodiments, X ⁸ Is N, and X ⁵ 、X ⁶ And X ⁷ Each of which is C.

In some embodiments, X ¹ To X ⁸ Each of which is C.

In some embodiments, each of part a and part B is independently selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, the aza variant comprises one N on the benzo ring. In some embodiments, the aza variant comprises one N on the benzo ring and the N is bonded to Ir.

In some embodiments, part a is a single ring. In some embodiments, part a is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, moiety a is pyridine or imidazole.

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

In some embodiments, part B is a single ring. In some embodiments, part B is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole. In some embodiments, moiety B is pyridine or imidazole.

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

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

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

In some embodiments, each of part a and part B may independently be a polycyclic fused ring structure comprising at least five fused rings. In some embodiments, the polycyclic fused ring structure comprises four 6-membered rings and one 5-membered ring or three 6-membered rings and two 5-membered rings. In some embodiments comprising two 5-membered rings, the 5-membered rings are fused together. In some embodiments comprising two 5-membered rings, the 5-membered rings are separated by at least one 6-membered ring. In some embodiments having one 5-membered ring, the 5-membered ring is fused to a ring coordinated to Ir, the second 6-membered ring is fused to the 5-membered ring, the third 6-membered ring is fused to the second 6-membered ring, and the fourth 6-membered ring is fused to the third 6-membered ring.

In some embodiments, each of part a and part B can independently be an aza form of the polycyclic fused ring described above. In some such embodiments, each of moieties a and B may independently contain exactly one aza N atom. In some such embodiments, each of moieties a and B contains exactly two aza N atoms, which may be in one ring or in two different rings. In some such embodiments, the ring having the aza N atom is separated from the metal M atom by at least two other rings. In some such embodiments, the ring having the aza N atom is separated from the Ir atom by at least three other rings. In some such embodiments, each of the ortho positions to the aza N atom is substituted.

In some embodiments, Y is selected from the group consisting of O, S and Se. In some embodiments, Y is not O. In some embodiments, Y is O.

In some embodiments, Y is selected from the group consisting of BR, NR, and PR. In some embodiments, Y is selected from the group consisting of: p (O) R, C = O, C = S, C =se, c=nr ', c=cr' R ", s=o and SO ₂ . At the position ofIn some embodiments, Y is CR. In some embodiments, Y is selected from the group consisting of: BRR ', CRR', siRR ', and GeRR'.

In some embodiments, R ^1& 、R ^2& 、R ^3& 、R ^4& And R is ^5& At least one of which is a germyl group.

In some embodiments, R ^1& 、R ^2& 、R ^3& 、R ^4& And R is ^5& Is aryl or heteroaryl, and the aryl or heteroaryl is substituted with a substituent comprising at least one germyl group. In some such embodiments, at least one germyl group is substituted with formula I&Or formula II&Is substituted by the bond para-position of the structure. In some such embodiments, the aryl or heteroaryl is substituted with at least two substituents comprising germyl. In some such embodiments, the aryl or heteroaryl is substituted with at least two substituents that are germyl.

At least one R ^1& 、R ^2& 、R ^3& 、R ^4& And R is ^5& In some embodiments which are aryl or heteroaryl, with aryl or heteroaryl and formula I &Or formula II&At least one position ortho to the bond between the structures of (a) is not H or D. In some such embodiments, an aryl or heteroaryl group is described as having formula I&Or formula II&At least one position ortho to the bond between the structures of (a) is selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof or partially or fully deuterated variants thereof.

In some embodiments, R ^1& 、R ^2& 、R ^3& 、R ^4& And R is ^5& Is aryl or heteroaryl, and the aryl or heteroaryl is substituted with at least one germyl group. In some embodiments, R ^1& 、R ^2& 、R ^3& 、R ^4& And R is ^5& Is phenyl substituted with at least one germyl group. In some such embodiments, the phenyl substituted with germyl groups is further substituted.

In some embodiments of the present invention, in some embodiments,at least one R ^1& 、R ^2& 、R ^3& 、R ^4& And R is ^5& Comprising a triphenylgermyl or trimethylgermyl group. In some embodiments, at least one R ^1& 、R ^2& 、R ^3& 、R ^4& And R is ^5& Is triphenyl-germanyl or trimethyl-germanyl.

In some embodiments, at least one R ^1& 、R ^2& Or R is ^3& Comprises at least one germyl group. In some embodiments, R ^1& 、R ^2& And R is ^3& Comprises at least one germanyl group.

In some embodiments, at least one R ^1& 、R ^2& Or R is ^3& Is a germyl group. In some embodiments, R ^1& 、R ^2& Or R is ^3& At least two of which are germanyl groups.

In some embodiments, only one R ^1& 、R ^2& Or R is ^3& Comprises at least one germyl group. In some embodiments, R ^1& 、R ^2& Or R is ^3& Comprising at least one germyl group.

In some embodiments, at least one R ^1& Comprises at least one germyl group. In some embodiments, at least two R ^1& Comprises at least one germyl group.

In some embodiments, at least one R ^2& Comprises at least one germyl group. In some embodiments, at least two R ^2& Comprises at least one germyl group.

In some embodiments, at least one R ^3& Comprises at least one germyl group. In some embodiments, at least two R ^3& Comprises at least one germyl group.

In some embodiments, two R ^1& Fused to form a 5-or 6-membered ring. In some such embodiments, the 5-or 6-membered is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazolePyrazole, pyrrole, oxazole, furan, thiophene, triazole and thiazole.

In some embodiments, Z ³ Is N, part A is non-condensed pyridine, and R is para to N-Ir bond ³ Comprises at least one germyl group.

In some embodiments, Z ³ Is N; part a is imidazole, benzimidazole or aza-benzimidazole; and R bonded to another N of the imidazole moieties ^3& Comprises at least one germyl group.

In some embodiments, at least one R ^4& Or R is ^5& Is a germyl group. In some embodiments, R ^4& And R is ^5& At least two of which are germanyl groups.

In some embodiments, only one R ^4& Or R is ^5& Comprises at least one germyl group. In some embodiments, at least two R ^4& Or R is ^5& Comprises at least one germyl group.

In some embodiments, at least one R ^4& Comprises at least one germyl group. In some embodiments, at least two R ^4& Comprises at least one germyl group.

In some embodiments, at least one R ^5& Comprises at least one germyl group. In some embodiments, at least two R ^5& Comprises at least one germyl group.

In some embodiments, Z ² Is N, part B is a non-condensed pyridine, and is combined with Z ¹ R of para-position ^4& Comprises at least one germyl group. In some embodiments, Z ² Is N, part B is a non-condensed pyridine, and is combined with Z ¹ R of para-position ^4& Is a germyl group.

In some embodiments, Z ² Is N, part B is a non-condensed pyridine, and is combined with Z ² R of para-position ^4& Comprises at least one germyl group. In some embodiments, Z ² Is N, part B is a non-condensed pyridine, and is combined with Z ² R of para-position ^4& Is a germyl group.

In some embodiments, Z ² Is N; a part (C)B is imidazole, benzimidazole or aza-benzimidazole; and R bonded to another N of the imidazole moieties ^4& Comprises at least one germyl group.

In some embodiments, the compound comprises one or more electron withdrawing groups. In some embodiments, the electron withdrawing group generally comprises one or more highly electronegative elements including, but not limited to, fluorine, oxygen, sulfur, nitrogen, chlorine, and bromine.

In some embodiments of the compounds, the electron withdrawing group has a Hammett constant (Hammett constant) greater than 0. In some embodiments, the Hammett constant of the electron withdrawing group is 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.

In some embodiments, the electron withdrawing group is selected from the group consisting of the structures of list EWG1 as defined herein.

In some embodiments, the electron withdrawing group is selected from the group consisting of structures of list EWG2 as defined herein.

In some embodiments, the electron withdrawing group is selected from the group consisting of the structures of list EWG3 as defined herein.

In some embodiments, the electron withdrawing group is selected from the group consisting of structures of list EWG4 as defined herein.

In some embodiments, the electron withdrawing group is a pi-electron deficient electron withdrawing group as defined herein.

In some embodiments, R ^1& 、R ^2& Or R is ^3& Is an electron withdrawing group from the list EWG1 as defined herein. In some embodiments, R ^1& 、R ^2& Or R is ^3& Is an electron withdrawing group from the list EWG2 as defined herein. In some embodiments, R ^1& 、R ^2& Or R is ^3& Is an electron withdrawing group from the list EWG3 as defined herein. In some embodiments, R ^1& 、R ^2& Or R is ^3& At least one of which is an electron withdrawing group from the list EWG4 as defined herein. In some embodiments, R ^1& 、R ^2& Or R is ^3& Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments, at least one R ^1& Is an electron withdrawing group from the list EWG1 as defined herein. In some embodiments, at least one R ^1& Is an electron withdrawing group from the list EWG2 as defined herein. In some embodiments, at least one R ^1& Is an electron withdrawing group from the list EWG3 as defined herein. In some embodiments, at least one R ^1& Is an electron withdrawing group from the list EWG4 as defined herein. In some embodiments, at least one R ^1& Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments, at least one R ^2& Is an electron withdrawing group from the list EWG1 as defined herein. In some embodiments, at least one R ^2& Is an electron withdrawing group from the list EWG2 as defined herein. In some embodiments, at least one R ^2& Is an electron withdrawing group from the list EWG3 as defined herein. In some embodiments, at least one R ^2& Is an electron withdrawing group from the list EWG4 as defined herein. In some embodiments, at least one R ^2& Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments, at least one R ^3& Is an electron withdrawing group from the list EWG1 as defined herein. In some embodiments, at least one R ^3& Is an electron withdrawing group from the list EWG2 as defined herein. In some embodiments, at least one R ^3& Is an electron withdrawing group from the list EWG3 as defined herein. In some embodiments, at least one R ^3& Is an electron withdrawing group from the list EWG4 as defined herein. In some embodiments, at least one R ^3& Is an electron withdrawing group from a list Pi-EWG as defined herein.

In one placeIn some embodiments, at least one L _A Is an electron withdrawing group from the list EWG1 as defined herein. In some embodiments, at least one L _A Is an electron withdrawing group from the list EWG2 as defined herein. In some embodiments, at least one L _A Is an electron withdrawing group from the list EWG3 as defined herein. In some embodiments, at least one L _A Is an electron withdrawing group from the list EWG4 as defined herein. In some embodiments, at least one L _A Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments, at least one L _B Is an electron withdrawing group from the list EWG1 as defined herein. In some embodiments, at least one L _B Is an electron withdrawing group from the list EWG2 as defined herein. In some embodiments, at least one L _B Is an electron withdrawing group from the list EWG3 as defined herein. In some embodiments, at least one L _B Is an electron withdrawing group from the list EWG4 as defined herein. In some embodiments, at least one L _B Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments, at least one L _C Is an electron withdrawing group from the list EWG1 as defined herein. In some embodiments, at least one L _C Is an electron withdrawing group from the list EWG2 as defined herein. In some embodiments, at least one L _C Is an electron withdrawing group from the list EWG3 as defined herein. In some embodiments, at least one L _C Is an electron withdrawing group from the list EWG4 as defined herein. In some embodiments, at least one L _C Is an electron withdrawing group from a list Pi-EWG as defined herein.

In some embodiments, each of moieties a and B is a non-fused pyridine ring, at least one R ^1& Or R is ^2& Is a germyl group, and X ⁵ To X ⁸ At least one of which is N.

In some embodiments, each of part A and part BOne being a non-condensed pyridine ring, at least one R ^1& Or R is ^2& Is germyl and Y is not O.

In some embodiments, X ⁵ Is C and is bonded to X ⁵ R of (2) ^1& Selected from the group consisting of: hydrogen, deuterium, methyl, phenyl, silane groups, germanyl groups, and combinations thereof.

In some embodiments, bonded to X ⁵ R of (2) ^1& Comprising a cyano group. In some embodiments, bonded to X ⁵ R of (2) ^1& Is cyano.

In some embodiments, bonded to X ⁶ R of (2) ^1& Comprising a cyano group. In some embodiments, bonded to X ⁶ R of (2) ^1& Is cyano.

In some embodiments, bonded to X ⁷ R of (2) ^1& Comprising a cyano group. In some embodiments, bonded to X ⁷ R of (2) ^1& Is cyano.

In some embodiments, bonded to X ⁸ R of (2) ^1& Comprising a cyano group. In some embodiments, bonded to X ⁸ R of (2) ^1& Is cyano.

In some embodiments, at least one R ^1& 、R ^2& 、R ^3& 、R ^4& Or R is ^5& A portion comprising a member selected from the group consisting of:

in some embodiments, at least one R ^1& Not hydrogen or cyano. In some embodiments, at least one R ^1& Not hydrogen, deuterium or cyano.

In some embodiments, two R ^1& Joined or fused to form a ring.

In some embodiments, at least one R ^2& Is not hydrogen. In some embodiments, at least one R ^2& Not hydrogen or deuterium.

In some embodiments, two R ^2& Joined or fused to form a ring.

In some embodiments, at least one R ^3& Is not hydrogen. In some embodiments, at least one R ^3& Not hydrogen or deuterium.

In some embodiments, at least one R ^3& Comprising at least two aryl or heteroaryl moieties that are not fused together. In some embodiments, at least one R ^3& Comprising at least two phenyl moieties that are not fused together.

In some embodiments, at least one R ^3& Comprising at least three aryl or heteroaryl moieties that are not fused together. In some embodiments, at least one R ^3& Comprising at least three phenyl moieties that are not fused together.

In some embodiments, at least one R ^4& Is not hydrogen. In some embodiments, at least one R ^4& Not hydrogen or deuterium.

In some embodiments, moiety B is a 6-membered ring, and is bonded to Z ¹ R of para-position ^4& Not hydrogen or deuterium. In some embodiments, moiety B is a 6-membered ring, and is bonded to Z ¹ R of para-position ^4& Comprising at least one of F, alkyl or aryl. In some embodiments, moiety B is a 6-membered ring, and is bonded to Z ¹ R of para-position ^4& Comprises a germyl group. In some embodiments, moiety B is a 6-membered ring, and is bonded to Z ¹ R of para-position ^4& Comprises a germyl group.

In some embodiments, at least one R ^4& Comprising an aryl group.

In some embodiments, at least one R ^5& Is not hydrogen. In some embodiments, at least one R ^5& Not hydrogen or deuterium.

In some embodiments, bonded to X ³ R of (2) ^5& Not hydrogen or deuterium. In some embodiments, bonded to X ³ R of (2) ^5& Comprising at least one of F, alkyl or aryl.

In some embodiments, two R ^5& Joined or fused to form a ring.

In some embodiments, ligand L _A Selected from the following list 1&Is composed of the following groups:

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wherein:

X ⁹ to X ¹² Is independently C or N;

Y ^A 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=cr ' R ", s= O, SO ₂ CR, CRR ', siRR ', and GeRR ';

each R, R ', R ' and R ' ^N Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with

Any two substituents may be fused or joined to form a ring.

In some embodiments, ligand L _A Selected from the following list 2&Is composed of the following groups:

wherein the method comprises the steps of

R ^D Mono-substituted selected from the group consisting of cyano, cyano-containing aryl, and cyano-containing heteroaryl;

R ^A 、R ^C and R is ^E Independently represents a single substitution to the maximum allowable substitution or no substitution;

each R ^A 、R ^C And R is ^E Independently hydrogen or selected from the group consisting of the general substituents defined hereinA substituent; and is also provided with

Any two substituents may be fused or joined to form a ring.

In some embodiments, R ^A 、R ^C Or R is ^E Comprises a germyl group. In some embodiments, at least one R ^A Is/comprises a germyl group. In some embodiments, at least one R ^C Comprises a germyl group. In some embodiments, at least one R ^E Comprises a germyl group.

In some embodiments, R ^A 、R ^C Or R is ^E At least one of which is a germyl group. In some embodiments, at least one R ^A Is a germyl group. In some embodiments, at least one R ^C Is or comprises a germyl group. In some embodiments, at least one R ^E Is a germyl group.

In some embodiments, ligand L _A Selected from the group consisting of: l (L) _Ai (E ^A )(R ^K )(R ^L )(R ^M )、L _A'm (E ^A )(R ^K )(R ^L )(R ^M )、L _AAn (E ^A )(R ^K )(R ^L )(R ^M ) And L _AA'o (E ^A )(R ^K )(R ^L )(R ^M ) Wherein i and m are each independently integers from 1 to 56, and n and o are each independently integers from 1 to 14;

wherein, when L _A Selected from the group consisting of L _Ai (E ^A )(R ^K )(R ^L )(R ^M ) When the group is formed, i is an integer of 1 to 56; e (E) ^A Selected from the group consisting of E1 to E40; r is R ^K And R is ^L Independently selected from the group consisting of R1 to R110; when i is 1, 2, 17, 45-48 or 51-56, R ^M Selected from the group consisting of R51 to R110; when i is 3-16, 18-44 or 49-50, R ^M Selected from the group consisting of R1 to R110; and is also provided with

Wherein L is _A1 (E1) (R1) (R1) (R51) to L _A56 (E40) (R110) each has a structure as defined in the following list 3 a:

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wherein, when L _A Selected from the group consisting of L _A'm (E ^A )(R ^K )(R ^L )(R ^M ) When in a group, m is an integer from 1 to 56; e (E) ^A Selected from the group consisting of E1 to E40; r is R ^K Selected from the group consisting of R71 to R110; r is R ^L Independently selected from the group consisting of R1 to R110; when m is 1, 2, 17 or 45-56, R ^M Selected from the group consisting of R51 to R110; when m is 3-16 or 18-44, R ^M Selected from the group consisting of R1 to R110; and is also provided with

L _A'1 (E1) (R71) (R1) (R51) to L _A'56 (E40) (R110) each has a structure as defined in the following list 3 b:

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wherein, when L _A Selected from the group consisting of L _AAn (E ^A )(R ^K )(R ^L )(R ^M ) When in a group, n is an integer from 1 to 14; e (E) ^A Selected from the group consisting of E1 to E40; r is R ^K Selected from the group consisting of R1 to R110; when n is 1, R ^L Selected from the group consisting of 51 to 110; when n is 2-14, R ^L Selected from the group consisting of 51 to 110; when n is 1 to 10, R ^M Selected from the group consisting of 1 to 110; when n is 11 to 14, R ^M Selected from the group consisting of 51 to 110; and L is _AA1 (E1) (R71) (R51) (R1) to L _AA14 (E40) (R110) each has a structure as defined in the following list 3 c:

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wherein, when L _A Selected from the group consisting of L _AA'o (E ^A )(R ^K )(R ^L )(R ^M ) When in a group, o is an integer from 1 to 14; e (E) ^A Selected from the group consisting of E1 to E40; r is R ^K Selected from the group consisting of R71 to R110; when o is 1, R ^L Selected from the group consisting ofA group consisting of 51 to 110; when o is 2-14, R ^L Selected from the group consisting of 51 to 90; when o is 1 to 10, R ^M Selected from the group consisting of 1 to 90; when o is 11 to 14, R ^M Selected from the group consisting of 51 to 110; and L is _AA'1 (E1) (R71) (R51) (R1) to L _AA'14 (E40) (R110) each has a structure as defined in the following list 3 d:

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Wherein R1 to R110 have the following list 4&A structure defined in (a): />

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wherein each of E1 to E40 has the following list 5&A structure defined in (a):

in some embodiments, the compound has a formula selected from the group consisting of: ir (L) _A ) ₃ 、r(L _A )(L _B ) ₂ 、Ir(L _A ) ₂ (L _B )、Ir(L _A ) ₂ (L _C ) And Ir (L) _A )(L _B )(L _C ) The method comprises the steps of carrying out a first treatment on the surface of the And wherein L is _A 、L _B And L _C Different from each other.

In some embodiments, L _B And L _C Each independently selected from the group consisting of the structures of the following list 6 as defined herein.

In some embodiments, L _B And L _C Each independently selected from the group consisting of the structures of the following list 8 as defined herein.

Wherein L is _A Selected from any L as described herein _A Comprising structure L _Ai (E ^A )(R ^K )(R ^L )(R ^M )、L _A'm (E ^A )(R ^K )(R ^L )(R ^M )、L _AAn (E ^A )(R ^K )(R ^L )(R ^M ) And L _AA'o (E ^A )(R ^K )(R ^L )(R ^M )；

Wherein k is an integer from 1 to 520;

wherein j is an integer from 1 to 1416;

the conditions are as follows:

when L _A Selected from the group consisting of L _Ai (E1)(R ^K )(R ^L )(R ^M ) K is 475 to 520 when the group is formedIs an integer of (2); and is also provided with

When L _A Selected from the group consisting of L _AAn (E1)(R ^K )(R ^L )(R ^M ) K is an integer from 475 to 490 when in the group;

when L _A Selected from the group consisting of L _AA'o (E1)(R ^K )(R ^L )(R ^M ) K is an integer from 1 to 490 when in the group;

Wherein k is an integer from 1 to 520; and each L _Bk Having a structure as defined in manifest 9 as defined herein;

Each L _Cj-II Has a structure based on the following formula:wherein for L _Cj-I And L _Cj-II Each L of (3) _Cj ，R ²⁰¹ And R is ²⁰² Each independently defined in the following list 10 as defined herein.

In some embodiments, the compound is selected from the group consisting of only L thereof _Bk A group consisting of those compounds corresponding to one of: l (L) _B1 、L _B2 、L _B18 、L _B28 、L _B38 、L _B108 、L _B118 、L _B122 、L _B124 、L _B126 、L _B128 、L _B130 、L _B132 、L _B134 、L _B136 、L _B138 、L _B140 、L _B142 、L _B144 、L _B156 、L _B158 、L _B160 、L _B162 、L _B164 、L _B168 、L _B172 、L _B175 、L _B204 、L _B206 、L _B214 、L _B216 、L _B218 、L _B220 、L _B222 、L _B231 、L _B233 、L _B235 、L _B237 、L _B240 、L _B242 、L _B244 、L _B246 、L _B248 、L _B250 、L _B252 、L _B254 、L _B256 、L _B258 、L _B260 、L _B262 And L _B264 、L _B265 、L _B266 、L _B267 、L _B268 、L _B269 And L _B270 。

In some embodiments, the compound is selected from the group consisting of having only the following L _Cj-I Those compounds of one of the structures of the ligand: />

in some embodiments, L _A Selected from the group consisting of: list 1&List 2&Structures of list 3a, list 3b, list 3c and list 3d, and L _B Selected from the group consisting of: list 6, list 8 and list 9. In some embodiments, L _A Selected from list 1&A group of, and L _B Selected from the group consisting of list 9. In some embodiments, L _A Selected from list 2&A group of, and L _B Selected from the group consisting of list 9. In some embodiments, L _A Selected from the group consisting of L as defined herein _A1 (E ^A )(R ^K )(R ^L )(R ^M ) To L _A44 (E ^A )(R ^K )(R ^L )(R ^M ) L of composition _Ai (E ^A )(R ^K )(R ^L )(R ^M ) Wherein i is an integer from 1 to 44, and L _B Selected from the group consisting of L _Bk List 9, wherein k is an integer from 1 to 520. In some embodiments, L _A Selected from the group consisting of L as defined herein _A'1 (E ^A )(R ^K )(R ^L )(R ^M ) To L _A'44 (E ^A )(R ^K )(R ^L )(R ^M ) L of composition _A'm (E ^A )(R ^K )(R ^L )(R ^M ) Wherein m is an integer from 1 to 44, and L _B Selected from the group consisting of L _Bk List 9, wherein k is an integer from 1 to 520. In some embodiments, L _A Selected from the group consisting of L as defined herein _AA1 (E ^A )(R ^K )(R ^L )(R ^M ) To L _AA10 (E ^A )(R ^K )(R ^L )(R ^M ) L of composition _AAn (E ^A )(R ^K )(R ^L )(R ^M ) Wherein n is an integer from 1 to 10, and L _B Selected from the group consisting of L _Bk List 9, wherein k is an integer from 1 to 520. In some casesIn embodiments, L _A Selected from the group consisting of L as defined herein _AA'1 (E ^A )(R ^K )(R ^L )(R ^M ) To L _AA'10 (E ^A )(R ^K )(R ^L )(R ^M ) L of composition _AA'o (E ^A )(R ^K )(R ^L )(R ^M ) Wherein o is an integer from 1 to 10, and L _B Selected from the group consisting of L _Bk List 9, wherein k is an integer from 1 to 520.

In some embodiments, the compound may be Ir (L _A ) ₂ (L _B )、Ir(L _A )(L _B ) ₂ Or Ir (L) _A )(L _B )(L _C ). In some of these embodiments, L _A May have formula I as defined herein. In some of these embodiments, L _A May be selected from the group consisting of: list 1 as defined herein&List 2&Structures of list 3a, list 3b, list 3c, and list 3 d. In some of these embodiments, L _B May be selected from the group consisting of the structures of manifest 6, manifest 8, and manifest 9 as defined herein. In some of these embodiments, L _C Can be selected from L as defined herein _CJ-I And L _CJ-II Is a group of structures. In some of these embodiments, the compound may be Ir (L _Ai (E ^A )(R ^K )(R ^L )(R ^M )) ₂ (L _B )、Ir(L _A'm (E ^A )(R ^K )(R ^L )(R ^M )) ₂ (L _B )、Ir(L _AAn (E ^A )(R ^K )(R ^L )(R ^M )) ₂ (L _B )、Ir(L _AA'o (E ^A )(R ^K )(R ^L )(R ^M )) ₂ (L _B )、Ir(L _Ai (E ^A )(R ^K )(R ^L )(R ^M ))(L _B ) ₂ 、Ir(L _A'm (E ^A )(R ^K )(R ^L )(R ^M ))(L _B ) ₂ 、Ir(L _AAn (E ^A )(R ^K )(R ^L )(R ^M ))(L _B ) ₂ 、Ir(L _AA'o (E ^A )(R ^K )(R ^L )(R ^M ))(L _B ) ₂ 、Ir(L _A ) ₂ (L _Bk )、Ir(L _A )(L _Bk ) ₂ 、Ir(L _Ai (E ^A )(R ^K )(R ^L )(R ^M )) ₂ (L _Bk )、Ir(L _A'm (E ^A )(R ^K )(R ^L )(R ^M )) ₂ (L _Bk )、Ir(L _AAn (E ^A )(R ^K )(R ^L )(R ^M )) ₂ (L _Bk )、Ir(L _AA'o (E ^A )(R ^K )(R ^L )(R ^M )) ₂ (L _Bk )、Ir(L _Ai (E ^A )(R ^K )(R ^L )(R ^M ))(L _Bk ) ₂ 、Ir(L _A'm (E ^A )(R ^K )(R ^L )(R ^M ))(L _Bk ) ₂ 、Ir(L _AAn (E ^A )(R ^K )(R ^L )(R ^M ))(L _Bk ) ₂ 、Ir(L _AA'o (E ^A )(R ^K )(R ^L )(R ^M ))(L _Bk ) ₂ 、Ir(L _Ai (E ^A )(R ^K )(R ^L )(R ^M ))(L _Bk )(L _CJ-I )、Ir(L _A'm (E ^A )(R ^K )(R ^L )(R ^M ))(L _Bk )(L _CJ-I )、Ir(L _AAn (E ^A )(R ^K )(R ^L )(R ^M ))(L _Bk )(L _CJ-I )、Ir(L _AA'o (E ^A )(R ^K )(R ^L )(R ^M ))(L _Bk )(L _CJ-I )、Ir(L _Ai (E ^A )(R ^K )(R ^L )(R ^M ))(L _Bk )(L _CJ-II )、Ir(L _A'm (E ^A )(R ^K )(R ^L )(R ^M ))(L _Bk )(L _CJ-II )、Ir(L _AAn (E ^A )(R ^K )(R ^L )(R ^M ))(L _Bk )(L _CJ-II ) Or Ir (L) _AA'o (E ^A )(R ^K )(R ^L )(R ^M ))(L _Bk )(L _CJ-II )。

It should be understood that in the followingAnd L is equal to _Bk Combined L _Ai (E ^A )(R ^K )(R ^L )(R ^M ) In some embodiments, k may be 475 to 520. At the position of L _Bk Combined L _AAn (E ^A )(R ^K )(R ^L )(R ^M ) In some embodiments of (1), when E ^A In the case of CN, k may be 475 to 490. At the position of L _Bk Combined L _AA'o (E ^A )(R ^K )(R ^L )(R ^M ) In some embodiments of (1), when E ^A In the case of CN, k may be 1 to 490.

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It is understood that two substituents of the same molecule as described throughout this disclosure may be joined or fused into a ring, so long as it is chemically feasible.

C. OLED and device of the present disclosure

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

In some embodiments, an OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a first ligand L as described herein having formula I _A Or a compound of formula III.

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

In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene comprising a benzofused thiophene or benzofused furan, wherein any substituent in the host is a non-fused substituent independently selected from the group consisting of: c (C) _n H _2n+1 、OC _n H _2n+1 、OAr ₁ 、N(C _n H _2n+1 ) ₂ 、N(Ar ₁ )(Ar ₂ )、CH＝CH-C _n H _2n+1 、C≡CC _n H _2n+1 、Ar ₁ 、Ar ₁ -Ar ₂ 、C _n H _2n -Ar ₁ Or unsubstituted, wherein n is an integer from 1 to 10; and wherein Ar is ₁ With Ar ₂ Independently selected from the group consisting of: benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

In some embodiments, the organic layer may further comprise a host, wherein the host comprises at least one chemical group selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ2-benzo [ d ] benzo [4,5] imidazo [3,2-a ] imidazole, 5, 9-dioxa-13 b-boronaphtho [3,2,1-de ] anthracene, triazine, borane, silane groups, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo [ d ] benzo [4,5] imidazo [3,2-a ] imidazole, and aza- (5, 9-dioxa-13 b-boronaphtho [3,2,1-de ] anthracene.

In some embodiments, the subject may be selected from a subject group 1 consisting of:

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wherein:

X ¹ to X ²⁴ Is independently C or N;

l' is a direct bond or an organic linking group;

each Y ^A Independently selected from the group consisting of: no 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 represents mono-substitution to maximum substitution or no substitutionSubstitution;

each R, R', R ^A '、R ^B '、R ^C '、R ^D '、R ^E '、R ^F ' and R ^G ' independently is hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanyl, seleno, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, borane, and combinations thereof;

R ^A '、R ^B '、R ^C '、R ^D '、R ^E '、R ^F ' and R ^G Adjacent two of the' are optionally joined or fused to form a ring.

In some embodiments, the subject may be selected from a subject group 2 consisting of:

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and combinations thereof.

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

In some embodiments, the emissive layer may include two hosts: a first body and a second body. In some embodiments, the first body is a hole transporting body and the second body is an electron transporting body. In some embodiments, the first host and the second host may form an exciplex.

In some embodiments, a compound as described herein may be a sensitizer; wherein the device may further comprise a recipient; and wherein the receptor may be selected from the group consisting of: fluorescent emitters, delayed fluorescent emitters, and combinations thereof.

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

In some embodiments, the emissive region may comprise a first ligand L having formula I as described herein _A A compound of formula (III) or a compound of formula (III).

In some embodiments, at least one of the anode, cathode, or new layer disposed over the organic emissive layer serves as the enhancement layer. The enhancement layer includes a plasmonic material exhibiting surface plasmon resonance, the plasmonic material non-radiatively coupled to the emitter material and transferring excited state energy from the emitter material to a non-radiative mode of surface plasmon polaritons. The enhancement layer is disposed no further than a threshold distance from the organic emissive layer, wherein the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer, and the threshold distance is where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the enhancement layer on an opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the emission layer from the enhancement layer, but is still able to outcouple energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered into free space as photons. In other embodiments, energy is scattered from surface plasmon modes of the device into other modes, such as, but not limited to, an organic waveguide mode, a substrate mode, or another waveguide mode. If the energy is scattered to the non-free space mode of the OLED, other outcoupling schemes may be incorporated to extract the energy into free space. In some embodiments, one or more intervening layers may be disposed between the enhancement layer and the outcoupling layer. Examples of intervening layers may be dielectric materials, including organic, inorganic, perovskite, oxides, and may include stacks and/or mixtures of these materials.

The enhancement layer alters the effective properties of the medium in which the emitter material resides, causing any or all of the following: reduced emissivity, altered emission linearity, altered emission intensity with angle, altered emitter material stability, altered OLED efficiency, and reduced OLED device roll-off efficiency. Placing the enhancement layer on the cathode side, the anode side, or both sides creates an OLED device that takes advantage of any of the effects described above. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, an OLED according to the present disclosure may also include any other functional layers common in OLEDs.

The enhancement layer may comprise a plasmonic material, an optically active super-structured material or a hyperbolic super-structured material. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material comprises at least one metal. In such embodiments, the metal may include at least one of the following: ag. Al, au, ir, pt, ni, cu, W, ta, fe, cr, mg, ga, rh, ti, ru, pd, in, bi, ca, alloys or mixtures of these materials, and stacks of these materials. Generally, a metamaterial is a medium composed of different materials, wherein the overall effect of the medium is different from the sum of its material portions. In particular, we define an optically active super-structured material as a material having both negative permittivity and negative permeability. On the other hand, hyperbolic metamaterials are anisotropic media in which the permittivity or permeability has different signs for different spatial directions. Optically active and hyperbolic metamaterials are very different from many other photonic structures, such as distributed Bragg reflectors (Distributed Bragg Reflector, "DBRs"), because the medium should exhibit uniformity in the direction of propagation over the length scale of the wavelength of light. Using terms that will be understood by those skilled in the art: the dielectric constant of a metamaterial in the propagation direction can be described by an effective dielectric approximation. Plasmonic and super-structured materials provide a method for controlling light propagation that can enhance OLED performance in a variety of ways.

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

In some embodiments, the outcoupling layer has wavelength-sized features that are periodically, quasi-periodically, or randomly arranged, or sub-wavelength-sized features that are periodically, quasi-periodically, or randomly arranged. In some embodiments, the outcoupling layer may be composed of a plurality of nanoparticles, and in other embodiments, the outcoupling layer is composed of a plurality of nanoparticles disposed over the material. In these embodiments, the outcoupling may be adjusted by at least one of the following means: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, changing the thickness of the reinforcing layer, and/or changing the material of the reinforcing layer. The plurality of nanoparticles of the device may be formed from at least one of: a metal, a dielectric material, a semiconductor material, a metal alloy, a mixture of dielectric materials, a stack or layering of one or more materials and/or a core of one type of material and a shell coated with another type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of: ag. Al, au, ir, pt, ni, cu, W, ta, fe, cr, mg, ga, rh, ti, ru, pd, in, bi, ca, alloys or mixtures of these materials, and stacks of these materials. The plurality of nanoparticles may have additional layers disposed over them. In some embodiments, the polarization of the emission may be adjusted using an outcoupling layer. Changing the size and periodicity of the outcoupling layer may select the type of polarization that preferentially outcouples to air. In some embodiments, the outcoupling layer also serves as an electrode of the device.

In yet another aspect, the present disclosure also provides a consumer product comprising an Organic Light Emitting Device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compound section of the disclosure.

In some embodiments, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a first ligand L as described herein having formula I _A Or a compound of formula III.

In some embodiments, the consumer product may be one of the following products: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cellular telephones, tablet computers, tablet handsets, personal Digital Assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro-displays with a diagonal of less than 2 inches, 3-D displays, virtual or augmented reality displays, vehicles, video walls comprising a plurality of displays tiled together, theatre or gym screens, phototherapy devices, and billboards.

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

Several OLED materials and configurations are described in U.S. patent nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

Initial OLEDs used emissive molecules that emitted light ("fluorescence") from a singlet state, as disclosed, for example, in U.S. patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in time frames less than 10 nanoseconds.

Recently, OLEDs have been demonstrated that have emissive materials that emit light from a triplet state ("phosphorescence"). Baldo et al, "efficient phosphorescent emission from organic electroluminescent devices (Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices)", nature, vol.395, 151-154,1998 ("Baldo-I"); and Bardo et al, "Very efficient green organic light emitting device based on electrophosphorescence (Very high-efficiency green organic light-emitting devices based on electrophosphorescence)", applied physical fast report (appl. Phys. Lett.), vol.75, stages 3,4-6 (1999) ("Bardo-II"), incorporated by reference in its entirety. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704, columns 5-6, which is incorporated by reference.

Fig. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. The device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a blocking layer 170. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 may be fabricated by depositing the layers in sequence. The nature and function of these various layers and example materials are described in more detail in U.S. Pat. No. 7,279,704 at columns 6-10, which is incorporated by reference.

Further examples of each of these layers are available. For example, a flexible and transparent linerThe bottom-anode combination is disclosed in U.S. patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F in a 50:1 molar ratio ₄ m-MTDATA of TCNQ, as disclosed in U.S. patent application publication No. 2003/0239980, which is incorporated by reference in its entirety. Examples of luminescent and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1:1, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of cathodes are disclosed in U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, that include composite cathodes having a thin layer of metal (e.g., mg: ag) containing an overlying transparent, electrically conductive, sputter-deposited ITO layer. The theory and use of barrier layers is described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of implanted layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.

Fig. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. The device 200 may be fabricated by depositing the layers in sequence. Because the most common OLED configuration has a cathode disposed above an anode, and the device 200 has a cathode 215 disposed below an anode 230, the device 200 may be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. Fig. 2 provides one example of how some layers may be omitted from the structure of the apparatus 100.

The simple layered structure illustrated in fig. 1 and 2 is provided by way of non-limiting example, and it should be understood that embodiments of the present disclosure may be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be obtained by combining the various layers described in different ways, or the layers may be 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 of the examples provided herein describe the various layers as comprising a single material, it should be understood that combinations of materials may be used, such as mixtures of host and dopant, or more generally, mixtures. Further, 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 emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to fig. 1 and 2.

Structures and materials not specifically described, such as OLEDs (PLEDs) comprising polymeric materials, such as disclosed in frank (Friend) et al, U.S. patent No. 5,247,190, which is incorporated by reference in its entirety, may also be used. By way of another example, an OLED with a single organic layer may be used. The OLEDs can be stacked, for example, as described in U.S. patent No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in fig. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Furster et al, and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Boolean et al, which are incorporated by reference in their entirety.

Any of the layers of the various embodiments may be deposited by any suitable method unless otherwise specified. Preferred methods for the organic layer include thermal evaporation, ink jet (as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, incorporated by reference in their entirety), organic vapor deposition (OVPD) (as described in U.S. Pat. No. 6,337,102, incorporated by reference in its entirety, furster et al), and deposition by organic vapor jet printing (OVJP, also known as Organic Vapor Jet Deposition (OVJD)), as described in U.S. Pat. No. 7,431,968, incorporated by reference in its entirety. Other suitable deposition methods include spin-coating and other solution-based processes. The solution-based process is preferably carried out under nitrogen or an inert atmosphere. For other layers, the preferred method includes thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding (as described in U.S. patent nos. 6,294,398 and 6,468,819, incorporated by reference in their entirety), and patterning associated with some of the deposition methods such as inkjet and Organic Vapor Jet Printing (OVJP). Other methods may also be used. The material to be deposited may be modified to suit the particular deposition method. For example, substituents such as alkyl and aryl groups that are branched or unbranched and preferably contain at least 3 carbons can be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 carbons or more may be used, and 3 to 20 carbons are a preferred range. A material with an asymmetric structure may have better solution processibility than a material with a symmetric structure because an asymmetric material may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

Devices fabricated according to embodiments of the present disclosure may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from harmful substances exposed to the environment including moisture, vapors and/or gases, etc. The barrier layer may be deposited on the substrate, electrode, under or beside the substrate, electrode, or on any other portion of the device, including the edge. The barrier layer may comprise a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include a composition having a single phase and a composition having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic compounds or organic compounds or both. Preferred barrier layers comprise a mixture of polymeric and non-polymeric materials, as described in U.S. patent No. 7,968,146, PCT patent application No. PCT/US2007/023098, and PCT/US2009/042829, which are incorporated herein by reference in their entirety. To be considered as a "mixture", the aforementioned polymeric and non-polymeric materials that make up the barrier layer should be deposited under the same reaction conditions and/or simultaneously. The weight ratio of polymeric material to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

Devices manufactured in accordance with embodiments of the present disclosure may be incorporated into a wide variety of electronic component modules (or units), which may be incorporated into a wide variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices (e.g., discrete light source devices or lighting panels), etc., that may be utilized by end user product manufacturers. The electronics assembly module may optionally include drive electronics and/or a power source. Devices manufactured in accordance with embodiments of the present disclosure may be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. Disclosed is a consumer product comprising an OLED comprising a compound of the present disclosure in an organic layer in the OLED. The consumer product should include any kind of product comprising one or more light sources and/or one or more of a certain type of visual display. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular telephones, tablet computers, tablet phones, personal Digital Assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro-displays (displays with a diagonal of less than 2 inches), 3-D displays, virtual or augmented reality displays, vehicles, video walls including a plurality of tiled displays, theatre or gym screens, phototherapy devices, and signs. Various control mechanisms may be used to control devices manufactured in accordance with the present disclosure, including passive matrices and active matrices. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as 18 ℃ to 30 ℃, and more preferably at room temperature (20-25 ℃), but can be used outside this temperature range (e.g., -40 ℃ to +80 ℃).

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.

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

In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, crimpable, collapsible, stretchable and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

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

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

In some embodiments, the compounds may be used as a phosphorus photosensitizer in an OLED, where one or more layers in the OLED contain receptors in the form of one or more fluorescent and/or delayed fluorescent emitters. In some embodiments, the compound may be used as a component of an exciplex to be used as a sensitizer. As a phosphorus photosensitizer, the compound must be able to transfer energy to the acceptor and the acceptor will emit energy or further transfer energy to the final emitter. The receptor concentration may be in the range of 0.001% to 100%. The acceptor may be in the same layer as the phosphorus photosensitizer or in one or more different layers. In some embodiments, the receptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission may be produced by any or all of the sensitizer, acceptor, and final emitter.

According to another aspect, a formulation comprising a compound described herein is also disclosed.

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

In yet another aspect of the invention, a formulation comprising the novel compounds disclosed herein is described. The formulation may comprise one or more components disclosed herein selected from the group consisting of: a solvent, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material.

The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure or monovalent or multivalent variants thereof. In other words, the compounds of the invention or monovalent or multivalent variants thereof may be part of a larger chemical structure. Such chemical structures may be selected from the group consisting of: monomers, polymers, macromolecules and supramolecules (also known as supramolecules). As used herein, "monovalent variant of a compound" refers to the same moiety as the compound but with one hydrogen removed and replaced with a bond to the rest of the chemical structure. As used herein, "multivalent variant of a compound" refers to a moiety that is identical to the compound but where 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 supramolecules, the compounds of the present invention may also be incorporated into supramolecular complexes without covalent bonds.

D. Combinations of compounds of the present disclosure with other materials

Materials described herein as suitable for use in particular layers in an organic light emitting device may be used in combination with a variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in combination with a wide variety of hosts, transport layers, barrier layers, implant layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one of ordinary skill in the art may readily review the literature to identify other materials that may be used in combination.

a) Conductive dopants:

the charge transport layer may be doped with a conductive dopant to substantially change its charge carrier density, which in turn will change its conductivity. Conductivity is increased by the generation of charge carriers in the host material and, depending on the type of dopant, a change in Fermi level (Fermi level) of the semiconductor can also be achieved. The hole transport layer may be doped with a p-type conductivity dopant, and an n-type conductivity dopant is used in the electron transport layer.

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

b)HIL/HTL：

The hole injection/transport material used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is generally used as a hole injection/transport material. Examples of materials include (but are not limited to): phthalocyanines or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; a fluorocarbon-containing polymer; a polymer having a conductive dopant; conductive polymers such as PEDOT/PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; metal oxide derivativesSuch as MoO _x The method comprises the steps of carrying out a first treatment on the surface of the p-type semiconducting organic compounds such as 1,4,5,8,9, 12-hexaazatriphenylene hexacarbonitrile; a metal complex; a crosslinkable compound.

Examples of aromatic amine derivatives for the HIL or HTL include, but are not limited to, the following general structures:

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Ar ¹ to Ar ⁹ Is selected from: a group consisting of, for example, the following aromatic hydrocarbon cyclic compounds: benzene, biphenyl, triphenylene, naphthalene, anthracene, benzene, phenanthrene, fluorene, pyrene, and the like,Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furandipyridine, benzothiophenopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units which are the same type or different types of groups selected from an aromatic hydrocarbon ring group and an aromatic heterocyclic group and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each Ar may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, ring Alkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, ar ¹ To Ar ⁹ Independently selected from the group consisting of:

wherein k is an integer from 1 to 20; x is X ¹⁰¹ To X ¹⁰⁸ Is C (including CH) or N; z is Z ¹⁰¹ Is NAr ¹ O or S; ar (Ar) ¹ Having the same groups as defined above.

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

wherein Met is a metal that may have an atomic weight greater than 40; (Y) ¹⁰¹ -Y ¹⁰² ) Is a bidentate ligand, Y ¹⁰¹ And Y ¹⁰² Independently selected from C, N, O, P and S; l (L) ¹⁰¹ Is an auxiliary ligand; k' is an integer value of 1 to the maximum number of ligands that can be attached to the metal; and k' +k "is the maximum number of ligands that can be attached to the metal.

In one aspect, (Y) ¹⁰¹ -Y ¹⁰² ) Is a 2-phenylpyridine derivative. In another aspect, (Y) ¹⁰¹ -Y ¹⁰² ) Is a carbene ligand. In another aspect, met is selected from Ir, pt, os, and Zn. In another aspect, the metal complex has a chemical structure as compared to an Fc ⁺ The minimum oxidation potential in solution of less than about 0.6V for Fc coupling.

Non-limiting examples of HIL and HTL materials that can be used in an OLED in combination with the materials disclosed herein are exemplified with references disclosing those materials as follows: CN, DE, EP EP, JP07-, JP EP, EP JP07-, JP US, US US, WO US, US WO, WO.

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c)EBL：

An Electron Blocking Layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a barrier layer in a device may result in substantially higher efficiency and/or longer lifetime than a similar device lacking such a barrier layer. Furthermore, a blocking layer may be used to limit the 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 higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as used in one of the hosts described below.

d) A main body:

the light-emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as a light-emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria are met.

Examples of metal complexes used as hosts preferably have the general formula:

wherein Met is goldBelongs to the genus; (Y) ¹⁰³ -Y ¹⁰⁴ ) Is a bidentate ligand, Y ¹⁰³ And Y ¹⁰⁴ Independently selected from C, N, O, P and S; l (L) ¹⁰¹ Is another ligand; k' is an integer value of 1 to the maximum number of ligands that can be attached to the metal; and k' +k "is the maximum number of ligands that can be attached to the metal.

In one aspect, the metal complex is:

wherein (O-N) is a bidentate ligand having a metal coordinated to the O and N atoms.

In another aspect, met is selected from Ir and Pt. In another aspect, (Y) ¹⁰³ -Y ¹⁰⁴ ) Is a carbene ligand.

In one aspect, the host compound contains at least one selected from the group consisting of: a group consisting of, for example, the following aromatic hydrocarbon cyclic compounds: benzene, biphenyl, triphenylene, tetramethylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furandipyridine, benzothiophenopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and a group of 2 to 10 cyclic building blocks, said The cyclic structural unit is the same type or different types of groups selected from the group consisting of an aromatic hydrocarbon ring group and an aromatic heterocyclic group and is bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each option in each group may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

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

wherein R is ¹⁰¹ Selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has a similar definition as Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20. X is X ¹⁰¹ To X ¹⁰⁸ Independently selected from C (including CH) or N. Z is Z ¹⁰¹ And Z ¹⁰² Independently selected from NR ¹⁰¹ O or S.

Non-limiting examples of host materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: US, WO WO, WO-based US, WO WO, US, US and US,

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e) Other emitters:

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

Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: CN, EB, EP1239526, EP, JP, KR TW, US20010019782, US TW, US20010019782, US US, US US, WO US, US US, WO.

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f)HBL：

A Hole Blocking Layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a barrier layer in a device may result in substantially higher efficiency and/or longer lifetime than a similar device lacking the barrier layer. Furthermore, a blocking layer may be used to limit the emission to a desired area of the OLED. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.

In one aspect, the compound used in the HBL contains the same molecules or the same functional groups as used in the host described above.

In another aspect, the compound used in the HBL contains in the molecule at least one of the following groups:

wherein k is an integer from 1 to 20; l (L) ¹⁰¹ Is another ligand, and k' is an integer from 1 to 3.

g)ETL：

An Electron Transport Layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complex or organic compound may be used as long as it is generally used to transport electrons.

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

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

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

wherein (O-N) or (N-N) is a bidentate ligand having a metal coordinated to atom O, N or N, N; l (L) ¹⁰¹ Is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

Non-limiting examples of ETL materials that can be used in an OLED in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

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h) Charge Generation Layer (CGL)

In tandem or stacked OLEDs, CGL plays a fundamental role in performance, consisting of n-doped and p-doped layers for injecting electrons and holes, respectively. Electrons and holes are supplied by the CGL and the electrode. Electrons and holes consumed in the CGL are refilled with electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n and p conductivity dopants used in the transport layer.

In any of the above mentioned compounds used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. The minimum amount of deuterated hydrogen in the compound is selected from the group consisting of: 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% and 100%. Thus, any of the specifically listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, and the like, can be in their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (e.g., without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc.) can also be in their non-deuterated, partially deuterated, and fully deuterated forms.

It should be understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention. The invention as claimed may thus include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that the various theories as to why the present invention works are not intended to be limiting.

Experimental data

Synthesis of Compound 1 of the present invention

To a 100mL round bottom flask was added 7- (4- (tert-butyl) naphthalen-2-yl) -3-methyl-2- (4- (trimethylgermyl) phenyl) thieno [2,3-c ] pyridine (1.766 g,3.37 mmol), iridium chloride (0.54 g,1.531 mmol), 2-ethoxyethanol (39 mL) and water (13.00 mL). The reaction mixture was heated under nitrogen at reflux overnight. After the reaction, the mixture was diluted with methanol, the red solid was filtered and used directly in the next step. To a 100mL round bottom flask was added red solid from the previous step, 3, 7-diethylnonane-4, 6-dione (0.504 g,3.08 mmol), DCM (25 mL), methanol (25.00 mL) and finally potassium carbonate (0.426 g,3.08 mmol). The mixture was heated to 40 ℃ overnight under nitrogen. After the reaction, the mixture was diluted with Dichloromethane (DCM) and filtered through Celite and washed with DCM. After evaporation of the filtrate, the residue was purified on a silica gel column eluting with 30% DCM/heptane to give 1.38g of product.

Synthesis of Compound 2 of the present invention

Compound 2 of the present invention can be synthesized using the reaction of known starting material 1 with a germyl-containing borate, trimethyl (3- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) germane, which is obtainable using literature procedures reported in organometallic chemistry (j. Organomet. Chem.) 2003,671,113-119. Compound 2 of the present invention may then be obtained by the procedure disclosed according to US patent application publication No. 20200216481, and the entire contents of the above references are incorporated herein by reference.

Synthesis of 7-bromodibenzo [ b, d ] furan-4-carbaldehyde

(2-fluoro-3-formylphenyl) boronic acid (11.0 g,65.5 mmol), 5-bromo-2-iodophenol (14 g,46.8 mmol), pd (Ph) ₃ P) ₄ (2.70 g,2.336 mmol) in dioxane (150 mL) and under N ₂ 2M aqueous sodium carbonate (58.5 mL,117 mmol) was added. The reaction mixture was then heated to 110 ℃ for 6 hours, then cooled to Room Temperature (RT), diluted with EtOAc (200 mL), washed with water (200 mL), the phases separated and the aqueous phase further extracted with EtOAc (200 mL). The combined organics were washed with brine (100 mL), dried over Na ₂ SO ₄ Drying, filtering andconcentrated in vacuo to give a brown oil. The crude product was purified by silica gel chromatography (silica dry load, 24g cartridge, 0-15% EtOAc/isohexane) to give 7-bromodibenzo [ b, d ] as a white solid]Furan-4-carbaldehyde (4.2 g,14.96mmol,31.9% yield).

Synthesis of 4-bromo-2, 6-diisopropyl-N- (2-nitrophenyl) aniline

KHMDS (1M in THF, 103mL,103 mmol) was added dropwise over 20 min to a mixture of 4-bromo-2, 6-diisopropylaniline (12 g,46.8 mmol) and 1-fluoro-2-nitrobenzene (5.5 mL,52.2 mmol) in dioxane (200 mL) at 0 ℃. The reaction mixture was stirred at room temperature for 16 hours, then quenched with water (200 mL) and extracted with ethyl acetate (3 x 100 mL). The organic layer was washed with brine (100 mL), and dried over Na ₂ SO ₄ Dried and concentrated under reduced pressure. The crude product was purified by silica gel chromatography (silica dry load, 120g cartridge, 0-15% EtOAc/isohexane) to give 4-bromo-2, 6-diisopropyl-N- (2-nitrophenyl) aniline (14.1 g,36.6mmol,78% yield) as an orange solid.

Synthesis of N1- (4-bromo-2, 6-diisopropylphenyl) benzene-1, 2-diamine) aniline

Zinc powder (10 g,153 mmol) was added to a solution of 4-bromo-2, 6-diisopropyl-N- (2-nitrophenyl) aniline (10 g,25.2 mmol) in methanol (100 mL) at room temperature followed by dropwise addition of a solution of ammonium chloride (6.73 g,126 mmol) in water (30 mL). The reaction mixture was stirred vigorously at 45 ℃ for 3 hours and filtered through a pad of celite. The celite pad was washed with EtOAc (100 mL) and the aqueous phase was extracted with EtOAc (3×150 mL). The combined organic layers were dried (MgSO ₄ ) And concentrated. The crude product was purified by silica gel chromatography (silica dry load, 220g cartridge, 0-20% EtOAc/isohexane) to give N1- (4-bromo) as a blue solid-2, 6-diisopropylphenyl) benzene-1, 2-diamine (15.83 g,43.3mmol,86% yield).

Synthesis of N1- (3, 5-diisopropyl- [1,1':4', 1' -biphenyl ] -4-yl) benzene-1, 2-diamine

To dioxane (75 mL) was added N1- (4-bromo-2, 6-diisopropylphenyl) benzene-1, 2-diamine (7.5 g,20.52 mmol), [1,1' -biphenyl) ]4-Ylboronic acid (8.5 g,42.9 mmol), 2M aqueous sodium carbonate (25 mL,50.0 mmol) and purging the reaction mixture with nitrogen for 5 min. Pd (Ph) was added ₃ P) ₄ (2.0 g,1.731 mmol) and the reaction mixture was purged with nitrogen for 5 min and then heated to 85 ℃ for 3 hours, cooled to RT, diluted with EtOAc (150 mL), washed with water (100 mL), the phases separated and the aqueous phase further extracted with EtOAc (200 mL). The combined organics were washed with brine (100 mL), dried over Na ₂ SO ₄ Dried, filtered and concentrated in vacuo to give a brown oil. The crude product was purified by silica gel chromatography (silica dry load, 220g cartridge, 0-50% EtOAc/isohexane) to give N1- (3, 5-diisopropyl- [1,1':4', 1' -diphenyl) as a blue solid]-4-yl) benzene-1, 2-diamine (6.5 g,14.68mmol,71.6% yield).

Synthesis of 2- (7-bromodibenzo [ b, d ] furan-4-yl) -1- (3, 5-diisopropyll- [1,1':4', 1' -benzil ] -4-yl) -1H-benzo [ d ] imidazole

Sodium bisulphite (6.5 g,62.5 mmol) was added to 7-bromodibenzo [ b, d]Furan-4-carbaldehyde (2.62 g,9.51 mmol) and N1- (3, 5-diisopropyl- [1,1':4',1 "-benzine)]A stirred solution of 4-yl) benzene-1, 2-diamine (4.0 g,9.51 mmol) in DMF (40 mL) and the reaction mixture heated at 120deg.C for 16 hours. The reaction mixture was poured into water (100 mL) and extracted with ethyl acetate (3×100 mL). The combined organics were combined with a similarly prepared batch, washed with 50% brine (2X 100 mL), and purified Na ₂ SO ₄ Dried and concentrated. The crude product was purified by flash chromatography (silica dry loading, 220g column, 0-50% ethyl acetate/isohexane) followed by further chromatography (silica dry loading, 220g column, 20-100% DCM/hexane) to give 2- (7-bromodibenzo [ b, d) as a white solid]Furan-4-yl) -1- (3, 5-diisopropyl- [1,1':4',1 "-benzine]-4-yl) -1H-benzo [ d ]]Imidazole (12.6 g, 65%).

Synthesis of 6- (1- (3, 5-diisopropyl- [1,1':4', 1' -biphenyl ] -4-yl) -1H-benzo [ d ] imidazol-2-yl) dibenzo [ b, d ] furan-3-carbonitrile

In a 100mL Schlenk flask (Schlenk flask) by vacuum-N ₂ Cycling three times 2- (7-bromodibenzo [ b, d)]Furan-4-yl) -1- (3, 5-diisopropyl- [1,1':4',1 "-benzine]-4-yl) -1H-benzo [ d ]]A mixture of imidazole (5.0 g,7.40 mmol), potassium hexacyanoferrate (II) trihydrate (1.561 g,3.70 mmol), potassium acetate (0.725 g,7.40 mmol), X-Phos Pd Gen2 (0.699 g,0.888 mmol) and X-Phos (0.881 g,1.850 mmol) was degassed. Dioxane (36 ml) and water (12 ml) were added and the reaction was heated to 100 ℃ for 96 hours. The crude material was purified by column chromatography eluting with 25-30% thf/heptane to yield 1.97g of a white solid.

Synthesis of 2- (4-fluorophenyl) -4, 5-bis (methyl-d) ₃ ) Pyridine (F-ppy)

To a solution of 2-bromo-4, 5-bis (methyl-d 3) pyridine (8.0 g,41.6 mmol) and (4-fluorophenyl) (l 4-alkylene) borane (6.45 g,52.1 mmol) in DME (210 ml) was added potassium carbonate (11.51 g,83 mmol) and water (70.0 ml). The reaction was purged with nitrogen for 15 minutes, then Pd (PPh ₃ ) ₄ (1.93 g,1.67 mmol). The reaction was heated under nitrogen in an oil bath set at 95 ℃ for 36 hours. The reaction mixture was extracted with EtOAc, followed byThe organic phase was washed 2 times with brine, dried over sodium sulfate, filtered and concentrated to a purple solid. The purple solid was purified by column chromatography eluting with 50/47.5/2.5 to 50/40/10 DCM/heptane/EtOAc to give 6.8g of the desired product as a white solid.

Synthesis [ (F-ppy) ₂ IrCl] ₂

A solution of 2- (4-fluorophenyl) -4, 5-bis (methyl-d 3) pyridine (6.79 g,32.8 mmol) and iridium (III) chloride hydrate (5.50 g,15.60 mmol) in 2-ethoxyethanol (120 mL) and water (40 mL) was treated with N ₂ Degassing for 10 minutes. The mixture was heated at 100℃for 18 hours. After cooling the reaction to room temperature, meOH was added and the solid was filtered and washed with MeOH to give 7.82g of a yellow solid.

Synthesis of solvate- [ (F-ppy) ₂ Ir]Otf

A solution of silver triflate (3.29 g,12.79 mmol) in MeOH (17.48 ml) was added to [ (F-ppy) in a flask wrapped with aluminum foil to avoid light ₂ IrCl] ₂ (7.80 g,6.09 mmol) in DCM (87 ml). The reaction mixture was stirred at room temperature for 18 hours. The solution was filtered through a celite pad, rinsing the flask and pad with dichloromethane (100 mL). The yellow filtrate was concentrated under reduced pressure and the solid was dried under vacuum at 40℃for 4 hours to give 7.84g of yellow solid.

Comparative example 2 Synthesis

To solvation [ (F-ppy) ₂ Ir]OTf (1.32 g,1.61 mmol) and 6- (1- (3, 5-diisopropyl- [1,1':4',1 ') -biphenyl)]-4-yl) -1H-benzo [ d ]]Imidazol-2-yl) dibenzo [ b, d]Furan-3-carbonitrile (1.00 g,1.61 mmol)To a solution of 2-ethoxyethanol (54 ml) was added 2, 6-lutidine (0.37 ml,3.22 mmol). The reaction was heated to 100 ℃ for 2 days. After cooling, volatiles were removed under vacuum and the resulting residue was eluted with toluene/heptane=80/20, purified by column chromatography to give 0.28g of a yellow solid.

Synthesis of 5-bromo-2- (4-fluorophenyl) pyridine

To a solution of 2, 5-dibromopyridine (50.0 g,211.1 mmol) and (4-fluorophenyl) boric acid (31.0 g,221.6 mmol) in acetonitrile (700 mL) and methanol (350 mL) was added potassium carbonate (72.9 g,527.7 mmol). The reaction was purged with nitrogen for 15 minutes, then Pd (PPh ₃ ) ₄ (12.2 g,10.6 mmol). The reaction was heated under nitrogen in an oil bath set at 50 ℃ for 24 hours. The reaction mixture was extracted with dichloromethane, followed by washing the organic phase with brine (100 ml), drying over sodium sulfate, filtration and concentration to a solid. The solid was purified by column chromatography eluting with 0 to 15% DCM/heptane to give 38g of the desired product as a white solid.

Synthesis of 2- (4-fluorophenyl) -5- (trimethylgermyl) pyridine (TMG-ppy-F)

N-butyllithium (3.5 mL,2.500 moles, 8.747 mmol) was added dropwise to a solution of 5-bromo-2- (4-fluorophenyl) pyridine (2.100 g,8.330 mmol) in anhydrous tetrahydrofuran (56 mL) under nitrogen at-78deg.C. After stirring the reaction at-78 ℃ for 5 minutes, chlorotrimethylgermane (2.552 g,2.06ml,16.66 mmol) was added and the reaction mixture was allowed to warm to room temperature and stirred for an additional 18 hours. The reaction mixture was extracted with ethyl acetate, followed by washing the organic phase with brine (50 ml), drying over sodium sulfate, filtration and concentration to a solid. The solid was purified by column chromatography eluting with 5 to 10% ethyl acetate/heptane to give 2.18g of white solid as the desired product.

Synthesis of [ (TMG-ppy-F) ₂ IrCl] ₂

By N ₂ A solution of 2- (4-fluorophenyl) -5- (trimethylgermyl) pyridine (2.18 g,7.52 mmol) and chloro (1, 5-cyclooctadiene) iridium (I) dimer (1.23 g,1.83 mmol) in 2-ethoxyethanol (10 mL) was degassed for 10 min. The mixture was heated at 100℃for 18 hours. After cooling the reaction to room temperature, water was added and the solid was filtered and washed with MeOH to give 2.68g of a yellow solid.

Synthesis of inventive example 3

To [ (TMG-ppy-F) ₂ IrCl] ₂ (0.88 g,0.55 mmol) and 6- (1- (3, 5-diisopropyl- [1,1':4',1 ') -diphenyl)]-4-yl) -1H-benzo [ d ]]Imidazol-2-yl) dibenzo [ b, d]To a solution of furan-3-carbonitrile (0.68 g,1.09 mmol) in a mixture of 2-ethoxyethanol (1 mL) and DMF (1 mL) was added potassium acetate (0.16 g,1.64 mmol). The reaction was heated to 140 ℃ for 24 hours. After cooling, volatiles were removed in vacuo and the resulting residue was photoisomerized in 15mL THF. Passing the reaction mixture throughThe pad was filtered, rinsed with dichloromethane until all yellow product eluted. The filtrate was concentrated under reduced pressure. The crude material was purified by silica gel chromatography eluting with 20% toluene/heptane. The residue was dissolved in dichloromethane (10 mL) and precipitated with methanol (20 mL). The solid was filtered and dried in a vacuum oven at 50 ℃ to give 0.23g of a yellow solid.

Device instance

Through high vacuum<10 ^-7 Tray) thermal evaporation to make the following device. The anode electrode isIndium Tin Oxide (ITO). Cathode is made of->Liq (lithium 8-hydroxyquinoline) and then +.>Al composition of (c). Immediately after manufacture, in a nitrogen glove box @<1ppm of H ₂ O and O ₂ ) All devices were enclosed with an epoxy-sealed glass cover and moisture absorbent was incorporated into the package interior. The organic stack of the device example consisted of the following in order from the ITO surface: / >LG101 (purchased from LG chemical company) as a Hole Injection Layer (HIL); />As a Hole Transport Layer (HTL); />As an Electron Blocking Layer (EBL); />An emissive layer (EML) containing RH and 18% RH2 as red hosts and 3% emitters; andliq (lithium 8-hydroxyquinoline) doped with 35% ETM was used as an Electron Transport Layer (ETL). Table 1 shows the thicknesses and materials of the device layers.

TABLE 1 device layer materials and thicknesses

The chemical structure of the device material is shown below:

the device was tested at the time of manufacture, both EL and JVL. For this purpose, the sample was measured at 10mA/cm using a 2 channel Keysight B2902A SMU ² Is energized and measured with a Photo Research PR735 spectroradiometer. Collecting the radiation intensity (W/str/cm) of 380nm to 1080nm ² ) And total integrated photon count. The device is then placed under a large area silicon photodiode for JVL scanning. At 10mA/cm using the device ² The lower integrated photon count converts the photodiode current into a photon count. Scanning voltage is 0 to equal to 200mA/cm ² Is set in the above-described voltage range. The EQE of the device is calculated using the total integrated photon count. All results are summarized in table 2. The voltages, EQE, and LT95 of the examples of the present invention are reported as relative numbers normalized to the results of the comparative examples.

Table 2.

Table 2 summarizes the performance of the electroluminescent devices. The inventive device (device 1) using inventive compound 1 as an emissive dopant exhibited a higher saturation red (λmax=621 nm) than device 2 (λmax=611 nm) using comparative compound 1. Colors with higher saturation are more popular in display applications. In addition, the device 1 was operated at 10mA/cm ² This provides higher efficiency and better device lifetime than device 2 while maintaining a similar operating voltage. These improvements are higher than any value attributable to experimental error, and the observed improvements are significant and unexpected. Thus, the inventive compound 1 can be used as an emissive dopant to improve OLED device performance.

Device instance

Through high vacuum<10 ^-7 Tray) thermal evaporation to make the following device. The anode electrode isIndium Tin Oxide (ITO). Cathode is made of->Liq (8-hydroxyquinoline lithium) and thereafter +.>Al composition of (c). All devices were placed in a nitrogen glove box immediately after manufacture<1ppm H ₂ O and O ₂ ) The package is sealed with an epoxy-sealed glass cover while incorporating a desiccant into the package interior. The organic stack of the device example consisted of the following in order starting from the ITO surface: />LG101 (from LG Chem) as a Hole Injection Layer (HIL); / >As a Hole Transport Layer (HTL); />As an Electron Blocking Layer (EBL); thickness->An emissive layer (EML); an emission layer containing an H host (H1) in a 6:4 ratio, an E host (H2) and 5 wt% green emitters; />Is used as a Hole Blocking Layer (HBL); +.o doped with 35% ETM>Liq (lithium 8-hydroxyquinoline) as ETL. The device structure is shown in table 3. The chemical structure of the device material is shown below. />

TABLE 3 device layer materials and thicknesses

After fabrication, the device was tested to measure EL and JVL. For this purpose, the sample was measured at 10mA/cm using a 2 channel Keysight B2902A SMU ² Is energized and measured using a Photo Research PR735 spectroradiometer. Collecting the radiation intensity (W/str/cm) of 380nm to 1080nm ² ) And total integrated photon count. The device is then placed under a large area silicon photodiode for JVL scanning. At 10mA/cm using the device ² The lower integrated photon count converts the photodiode current into a photon count. Scanning voltage is 0 to equal to 200mA/cm ² Is set in the above-described voltage range. The EQE of the device is calculated using the total integrated photon count. All results are summarized in table 3. Voltage, LE, EQE, PE and LT of inventive example (device 3) _97％ Is reported as relative numbers normalized to the results of the comparative example (device 4).

TABLE 4 results of the apparatus

Table 4 provides a summary of the properties of the electroluminescent devices of the materials. The inventive device (device 3) showed a purer green color with a peak wavelength of 522nm compared to the comparative device (device 4). Furthermore, the present examples show a narrower line shape with a FWHM of 52 nm. In general, the FWHM of phosphorescent emitter complexes is broad, typically equal to or higher than 55nm, as shown in the comparative examples herein. Achieving a narrow FWHM is a long sought-after goal. The narrower the FWHM, the better the color purity for display applications. As background information, an ideal line shape is a single wavelength (single line). As can be seen here, the compounds of the present invention having a germyl substituent can reduce the FWHM number by 3nm compared to the comparative compound. This is a significantly unexpected result. The compounds of the present invention have also blue shifted to more desirable blue colors, which can make the device more efficient and color purer. These improvements in value are higher than the values attributable to experimental error, and the observed improvements are significant. The performance improvement observed in the above data was unexpected. All the results show the importance of the compounds of the invention for use in OLEDs.

Claims

1. Ir (L) _A ) _p (L _B ) _q (L _C ) _r Wherein:

the first ligand L _A Having the formula IA structure;

ligand L _B Having the formula IIIs of a structure of (2);

ligand L _C Is a bidentate ligand;

p is 1 or 2; q is 0, 1 or 2; r is 0, 1 or 2;

p+q+r＝3；

X ¹ to X ⁸ And Z ¹ To Z ⁴ Is independently C or N;

y 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＝CR'R"、S＝O、SO ₂ CR, CRR ', siRR ', and GeRR ';

R ¹ 、R ² 、R ³ 、R ⁴ and R is ⁵ Independently represents a single substitution to the maximum allowable substitution or no substitution;

each R, R', R ¹ 、R ² 、R ³ 、R ⁴ And R is ⁵ Independently and separatelyIs hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, germanyl, and combinations thereof;

any two R, R', R ¹ 、R ² 、R ³ 、R ⁴ Or R is ⁵ May be joined or fused to form a ring, or to form a tetradentate or hexadentate ligand;

at least one R ¹ 、R ² 、R ³ 、R ⁴ Or R is ⁵ Comprises at least one germyl group; and is also provided with

At least one R ¹ Comprises cyano groups, provided that:

(1) If both rings A and B are non-condensed pyridine rings, and R ⁴ And R is ⁵ At least one of which is a germyl group, then (a) X ⁵ To X ⁸ At least one of which is N or (b) Y is other than O; and

(2) If X ⁵ C is then bonded to X ⁵ R of (2) ¹ Selected from the group consisting of: hydrogen, deuterium, cycloalkyl, methyl, phenyl, silane, germanyl, and combinations thereof.

2. The compound according to claim 1, wherein Z ¹ Or Z is ² One of which is N and the other is C; and/or

Wherein Z is ³ Or Z is ⁴ One of which is N and the other is C; and/or

Wherein X is ¹ To X ⁸ Each of which is C, or X ¹ To X ⁸ At least one of which is N.

3. The compound of claim 1, wherein each of part a and part B is independently selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene; and/or

Wherein two R ¹ Two R ² Or two R ⁵ Joining or fusing to form a ring; and/or

Wherein at least one R ³ Comprising at least two aryl or heteroaryl moieties that are not fused together.

4. The compound of claim 1, wherein at least one R ¹ 、R ² Or R is ³ Comprises at least one germyl group;

and/or at least one R ⁴ Or R is ⁵ Is a germyl group.

5. The compound according to claim 1, wherein Z ³ Is N, part A is a non-condensed pyridine, and R is para to the N-Ir bond ³ Comprises at least one germyl group; and/or wherein Z ² Is N, part B is a non-condensed pyridine, and is combined with Z ¹ Or Z is ² R of para-position ⁴ Comprises at least one germyl group.

6. The compound according to claim 1, wherein X ⁵ Is C and is bonded to X ⁵ R of (2) ¹ Selected from the group consisting of: hydrogen, deuterium, methyl, phenyl, silane, germanyl, and combinations thereof; and/or

Wherein is bonded to X ⁶ Or X ⁷ R of (2) ¹ Comprising a cyano group.

7. The method according to claim 1A compound wherein the ligand L _A Selected from the group consisting of:

wherein:

X ⁹ to X ¹² Is independently C or N;

Y ^A 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＝CR'R"、S＝O、SO ₂ CR, CRR ', siRR ', and GeRR ';

Each R, R ', R ' and R ' ^N Independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, germanyl, and combinations thereof; and is also provided with

Any two substituents may be fused or joined to form a ring.

8. The compound of claim 1, wherein the ligand L _A Selected from the group consisting of:

wherein the method comprises the steps of

each R ^A 、R ^C And R is ^E Independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, germanyl, and combinations thereof; and is also provided with

Any two substituents may be fused or joined to form a ring.

9. The compound of claim 1, wherein the ligand L _A Selected from the group consisting of: l (L) _Ai (E ^A )(R ^K )(R ^L )(R ^M )、L _A'm (E ^A )(R ^K )(R ^L )(R ^M )、L _AAn (E ^A )(R ^K )(R ^L )(R ^M ) And L _AA'o (E ^A )(R ^K )(R ^L )(R ^M ) Wherein i and m are each independently integers from 1 to 56, and n and o are each independently integers from 1 to 14;

wherein when L _A Selected from the group consisting of L _Ai (E ^A )(R ^K )(R ^L )(R ^M ) When the group is formed, i is an integer of 1 to 56; e (E) ^A Selected from the group consisting of E1 to E40; r is R ^K And R is ^L Independently selected from the group consisting of R1 to R110; when i is 1, 2, 17, 45 to 48 or 51 to 56, R ^M Selected from the group consisting of R51 to R110; when i is 3 to 16, 18 to 44 or 49 to 50, R ^M Selected from the group consisting ofA group consisting of R1 to R110; and wherein L is _A1 (E1) (R1) (R1) (R51) to L _A56 (E40) (R110) each has a structure defined as follows:

wherein when L _A Selected from the group consisting of L _A'm (E ^A )(R ^K )(R ^L )(R ^M ) When in a group, m is an integer from 1 to 56; e (E) ^A Selected from the group consisting of E1 to E40; r is R ^K Selected from the group consisting of R71 to R110; r is R ^L Independently selected from the group consisting of R1 to R110; when m is 1, 2, 17 or 45 to 56, R ^M Selected from the group consisting of R51 to R110; when m is 3 to 16 or 18 to 44, R ^M Selected from the group consisting of R1 to R110; and L is _A'1 (E1) (R71) (R1) (R51) to L _A'56 (E40) (R110) each has a structure defined as follows:

/>

wherein when L _A Selected from the group consisting of L _AAn (E ^A )(R ^K )(R ^L )(R ^M ) When in a group, n is an integer from 1 to 14, E ^A Selected from the group consisting of E1 to E40; r is R ^K Selected from the group consisting of R1 to R110; when n is 1, R ^L Selected from the group consisting of 51 to 110; when n is 2 to 14, R ^L Selected from the group consisting of 51 to 110; when n is 1 to 10, R ^M Selected from the group consisting of 1 to 110; when n is 11 to 14, R ^M Selected from the group consisting of 51 to 110; and L is _AA1 (E1) (R71) (R51) (R1) to L _AA14 (E40) (R110) each has a structure defined as follows:

wherein when L _A Selected from the group consisting of L _AA'o (E ^A )(R ^K )(R ^L )(R ^M ) Composed ofWhen in group; o is an integer of 1 to 14, E ^A Selected from the group consisting of E1 to E40; r is R ^K Selected from the group consisting of R71 to R110; when o is 1, R ^L Selected from the group consisting of 51 to 110; when o is 2 to 14, R ^L Selected from the group consisting of 51 to 110; when o is 1 to 10, R ^M Selected from the group consisting of 1 to 90; when o is 11 to 14, R ^M Selected from the group consisting of 51 to 110; and L is _AA'1 (E1) (R71) (R51) (R1) to L _AA'14 (E40) (R110) each has a structure defined as follows:

/>

wherein R1 to R110 have the structure defined as follows: />

/>

Wherein each of E1 to E40 has a structure as defined below:

10. the compound of claim 1, wherein the compound has a formula selected from the group consisting of: ir (L) _A ) ₃ 、Ir(L _A )(L _B ) ₂ 、Ir(L _A ) ₂ (L _B )、Ir(L _A ) ₂ (L _C ) And Ir (L) _A )(L _B )(L _C ) The method comprises the steps of carrying out a first treatment on the surface of the And wherein L is _A 、L _B And L _C Different from each other.

11. The compound of claim 1, wherein L _B And L _C Each independently selected from the group consisting of:

/>

wherein:

t is selected from the group consisting of: B. al, ga and In;

K ¹ ' selected from the group consisting of: single bond, O, S, NR _e 、PR _e 、BR _e 、CR _e R _f And SiR _e R _f ；

Y ¹ To Y ¹³ Independently selected from the group consisting of: c and N;

y' is selected from the group consisting of: BR (BR) _e 、BR _e R _f 、NR _e 、PR _e 、P(O)R _e 、O、S、Se、C＝O、

C＝S、C＝Se、C＝NR _e 、C＝CR _e R _f 、S＝O、SO ₂ 、CR _e R _f 、SiR _e R _f And GeR _e R _f ；

R _e And R is _f Can be fused or joined to form a ring;

each R _a 、R _b 、R _c And R is _d Independently represents a single substitution to a maximum allowable number of substitutions or no substitution;

R _a1 、R _b1 、R _c1 、R _d1 、R _a 、R _b 、R _c 、R _d 、R _e and R is _f Each of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, seleno alkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

R _a1 、R _b1 、R _c1 、R _d1 、R _a 、R _b 、R _c And R is _d Any two substituents of (a) may be fused or joined to form a ring or to form a multidentate ligand.

12. The compound according to claim 10, wherein the compound has the formula Ir (L _A ) ₃ Ir (L) _A )(L _Bk ) ₂ Ir (L) _A ) ₂ (L _Bk ) Ir (L) _A ) ₂ (L _Cj-I ) Or Ir (L) _A ) ₂ (L _Cj-II )，

Wherein L is _A Selected from any L as defined herein _A Comprising L _Ai (E ^A )(R ^K )(R ^L )(R ^M )、L _A'm (E ^A )(R ^K )(R ^L )(R ^M )、L _AAn (E ^A )(R ^K )(R ^L )(R ^M ) And L _AA'o (E ^A )(R ^K )(R ^L )(R ^M ) Is of a structure of (2);

wherein k is an integer from 1 to 520;

wherein j is an integer from 1 to 1416;

the conditions are as follows:

when L _A Selected from the group consisting of L _Ai (E1)(R ^K )(R ^L )(R ^M ) K is an integer from 475 to 520 when in the group; and is also provided with

wherein k is an integer from 1 to 520; and each L _Bk Has a structure as defined below: />

/>

Each L _Cj-II Has a structure based on the following formula:wherein for L _Cj-I And L _Cj-II Each L of (3) _Cj ，R ²⁰¹ And R is ²⁰² Each independently defined as follows:

/>

wherein R is ^D1 To R ^D246 The structure is as follows:

/>

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

/>

14. 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 the compound of claim 1.

15. A consumer product comprising an organic light emitting device, the organic light emitting device comprising:

an anode;

a cathode; and