CN116903670A

CN116903670A - Organic electroluminescent material and device

Info

Publication number: CN116903670A
Application number: CN202310418767.5A
Authority: CN
Inventors: 蔡瑞益; 亚力克西·鲍里索维奇·迪亚特金; 沃尔特·耶格尔; 皮埃尔·吕克·T·布德罗; 陈小凡; 辛卫春
Original assignee: Universal Display Corp
Current assignee: Universal Display Corp
Priority date: 2022-04-18
Filing date: 2023-04-18
Publication date: 2023-10-20

Abstract

The present application relates to organic electroluminescent materials and devices. There is provided a compound comprising formula IIs a first ligand L of (2) _A . In formula I, moiety a is a 5-or 6-membered ring; part B is a fused ring structure comprising at least four rings; k is a direct bond, O or S; z is Z ¹ And Z ² Is independently C or N; each R ^A And R is ^B Independently hydrogen or a general substituent; at least one R ^B Comprising cyclic or electron withdrawing groups; l (L) _A Coordinated to a metal M having an atomic mass of at least 40 and optionally coordinated to other ligands; and the ligand L _A Optionally linked to other ligands. Formulations, OLEDs and consumer products comprising the compounds are also provided.

Description

Organic electroluminescent material and device

Cross reference to related applications

The present application is part of the continued application as in U.S. patent application Ser. No. 18/058,461 (filed on day 23 of 11, 2022) and U.S. patent application Ser. No. 18/177,178 (filed on day 2 of 3, 2023). The present application claims priority from 35u.s.c. ≡119 (e) to the following U.S. provisional applications: 63/481,143 of day 23 of 2023, 63/476,204 of day 12 of 2022, 63/385,994 of day 5 of 2022, 63/385,730 of day 1 of 2022, 63/382,134 of day 3 of year 11, 63/417,746 of day 20 of year 2022, 63/408,686 of day 21 of year 2022, 63/408,357 of day 20 of year 2022, 63/407 of day 19 of year 2022, 981 of day 2022, 63/406,019 of day 13 of year 2022, 63/392,731 of day 27 of year 2022, 63/356 of day 28 of year 2022, 63/354 of day 23 of year 2022, 2022/21 of year 2022, and 63/357 of day 21 of year 2022, and 3 of year 2022 are all filed in the same manner as mentioned in the application of day 4, 63/357 of day, year 2, 2022, and 3, day 202, day 9, day 19 of year, and 3, day 15, 150 of the entire contents of the application are filed in the same order as mentioned.

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

In one aspect, the present disclosure provides a compound comprising the formulaIs a first ligand L of (2) _A . In formula I: part a is a 5-or 6-membered carbocyclic or heterocyclic ring; part B is a fused ring structure comprising at least three rings, each of which is independently a heterocycle or carbocycle; k is a direct bond, O or S; z is Z ¹ And Z ² Is independently C or N; r is R ^A And R is ^B Independently represents a single substitution to the maximum possible number of substitutions, or no substitution; each R ^A And R is ^B Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, boron, selenium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; any two R ^A Or R is ^B May be joined or fused to form a ring; at least one R ^B Comprising cyclic or electron withdrawing groups; l (L) _A Coordination with metal M; the metal M has an atomic mass of at least 40 and can coordinate with other ligands; and the ligand L _A OptionalIs linked to other ligands to form a tridentate, tetradentate, pentadentate or hexadentate ligand.

In another aspect, the present disclosure provides a formulation comprising a first ligand L having formula I as described herein _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 having formula I as described herein _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 "seleno" 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 "germanium group" refers to-Ge (R) _s ) ₃ A group wherein each R _s May be the same or different.

The term "boron group" means-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, alkynylAryl, 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 groups and 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, oxatriazole, dioxazole, 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, thienodipyridine, benzoselenophene dipyridine, dibenzofuran, dibenzoselenium, carbazole, indolocarbazole, benzimidazole, triazine, 1, 2-azaboron-1, 4-azaboron-nitrogen, boron-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, germanium, boron, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, seleno, 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, germanium, boron, 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, 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 with 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 can be 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 compound comprising the formulaIs a first ligand L of (2) _A . In formula I:

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

part B is a fused ring structure comprising at least three rings, each of which is independently a heterocycle or carbocycle;

k is a direct bond, O or S;

Z ¹ and Z ² Is independently C or N;

R ^A and R is ^B Independently represents a single substitution to the maximum possible number of substitutions, or no substitution;

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

any two R ^A Or R is ^B Can be connected withFused or fused to form a ring;

at least one R ^B Comprising cyclic or electron withdrawing groups;

L _A coordination with metal M;

the metal M has an atomic mass of at least 40 and can coordinate with other ligands; and is also provided with

The ligand L _A Optionally linked to other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands.

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

In some embodiments, at least one R comprising a cyclic or electron withdrawing group ^B Not with another R ^A Or R is ^B Joined or fused to form a 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, 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, 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 located on the benzo ring and the N is bonded to metal M.

In some embodiments, K may be a direct bond. In some embodiments, K may be O. In some embodiments, K may be S. It is to be understood that when K is O or S, Z ² Is C.

In some embodiments, when K is a direct bond and part a is an imidazole ring, then two R ^A And are not joined to form a 6-membered ring. In some embodiments, when K is a direct bond and part a is an imidazole ring, then two R ^A The phenyl ring is not formed by bonding. In some embodiments, when K is a direct bond and part a is an imidazole ring and one N atom of the imidazole ring coordinates to the metal, then two R ^A And are not joined to form a 6-membered ring. In some embodiments, when K is a direct bond and part a is an imidazole ring and one N atom of the imidazole ring coordinates to the metal, then two R ^A The phenyl ring is not formed by bonding. In some embodiments, when K is a direct bond and moiety a is a benzimidazole group and one N atom of the benzimidazole group coordinates to a metal, then moiety B is a polycyclic fused ring structure containing at least 5 rings. In some embodiments, when moiety a is a benzimidazole group and one N atom of the benzimidazole group coordinates to a metal, then the ring of moiety B that coordinates to the metal is not a benzene ring. In some embodiments, when L _A When part A of (2) is a benzimidazole group then L _A Does not form a metal complex with another ligand containing a substituted pyridine ring. In some embodiments, when L _A When part A of (2) is a benzimidazole group then L _A The metal complex is not formed with another ligand containing a silyl or germanium group substituted pyridine moiety. In some embodiments, when L _A When part A of (2) is a benzimidazole group then L _A The metal complex is not formed with another ligand containing a pyridine moiety substituted with a 3-silyl group or a 3-germanium group.

In some embodiments, part B comprises formulaWherein Y is selected from the group consisting of: BR ', BR ' R ", NR ', PR ', P (O) R ', 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 ", alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof. In some embodiments, each R' or R "is independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein.

In some embodiments including formula II, moiety B comprises at least two rings of formula II, wherein the at least two rings of formula II may be the same or different.

In some embodiments, moiety B comprises exactly three fused rings, each of which is independently a heterocycle or carbocycle. In some of such embodiments, two rings are 6 membered rings and one ring is a 5 membered ring. In some of such embodiments, the intermediate ring is a 5-membered ring. In some of such embodiments, moiety B may not be dibenzofuran. In some of such embodiments, each of the rings is independently a 5-or 6-membered aryl or heteroaryl. In some embodiments, each of the rings is independently selected from the group consisting of: phenyl, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.

In some embodiments, moiety B is a fused ring structure comprising at least five rings, each of which is independently a heterocycle or carbocycle.

In some embodiments, part B comprises at least four fused rings, and each of the at least four rings of part B is independently selected from the group consisting of: phenyl, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.

In some embodiments, part B comprises at least three six membered rings. In some embodiments, moiety B comprises at least three six membered rings each independently being phenyl or pyridine.

In some embodiments, part B comprises at least four six-membered rings. In some embodiments, moiety B comprises at least four six-membered rings that are each independently phenyl or pyridine.

In some embodiments, moiety B is a polycyclic fused ring structure. In some embodiments, moiety B is 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, part B is selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and aza variants thereof. In some such embodiments, moiety B may be further substituted at a position ortho or meta to 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, moiety B is 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, moiety B is 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, moiety B is independently an aza form of a fused ring as described above. In some such embodiments, moiety B independently contains exactly one aza N atom. In some such embodiments, moiety 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 Ir atom by at least two further rings. In some such embodiments, the ring having the aza N atom is separated from the Ir atom by at least three further rings. In some such embodiments, each ortho position to the aza N atom is substituted.

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

In some embodiments, at least one R ^A Not hydrogen and deuterium.

In some embodiments, at least one R ^B Is a cyclic group. In some embodiments, at least one R ^B Comprising aryl or heteroaryl groups. In some embodiments, at least one R ^B Comprising cycloalkyl or heterocycloalkyl, any of which may be substituted or unsubstituted.

In some embodiments, at least one R ^B Comprising at least one monocyclic group. In some embodiments, at least one R ^B Comprising fused polycyclic groups. In some of such embodiments, the fused polycyclic group may comprise all saturated carbocycles or heterocycles. In some of such embodiments, the fused polycyclic group may comprise all unsaturated carbocycles or heterocycles. In some of such embodiments, the fused polycyclic groups may comprise both saturated and unsaturated carbocycles or heterocycles. In some of such embodiments, the fused polycyclic group may comprise aryl and/or heteroaryl rings. In some of such embodiments, the fused polycyclic group may be naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, nitrogenHetero-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, phenanthridine, fluorene, and aza-fluorene. In some of such embodiments, the aza variant comprises one N located on the benzo ring. It is understood that all of the above fused polycyclic groups may be unsubstituted or further substituted.

In some embodiments, at least one R ^B Is an electron withdrawing group having a Hammett constant (Hammett constant) greater than 0. In some embodiments, at least one R ^B Is an electron withdrawing group having a Hammett constant equal to or greater than a value selected from the group consisting of: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 and 1.1. In these embodiments, the electron withdrawing group typically comprises one or more highly electronegative elements such as, but not limited to, fluorine, oxygen, sulfur, nitrogen, chlorine, and bromine.

In some embodiments, at least one R ^B Comprising an electron withdrawing group selected from the group consisting of the following list 1 or an electron withdrawing group selected from the group consisting of the following list 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) ₃ 、(R) ₂ CCN、(R) ₂ CCF ₃ 、CNC(CF ₃ ) ₂ BRR', substituted or unsubstituted dibenzoborolan, 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 oxazoleSubstituted or unsubstituted benzoxazoles, substituted or unsubstituted thiazoles, substituted or unsubstituted benzothiazoles, substituted or unsubstituted imidazoles, substituted or unsubstituted benzimidazoles, ketones, carboxylic acids, esters, nitriles, isonitriles, sulfinyl, sulfonyl, partially fluorinated and fully fluorinated alkyl, partially fluorinated and fully fluorinated aryl, partially fluorinated and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanates,

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 GeReRf', and each R, 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, R may be monosubstituted up to a maximum number of permissible substitutions or unsubstituted.

L of formula I _A In some embodiments of (2), at least one R ^B An electron withdrawing group selected from the group consisting of:

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in some embodiments, at least one R ^B An electron withdrawing group selected from the group consisting of:

in some embodiments, at least one R ^B Is an electron withdrawing group selected from the group consisting of: fluoride, perfluoroalkyl, perfluorocycloalkyl, perfluorovinyl, CN, SCN, SF ₅ And SCF ₃ 。

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: 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) ₃ BRR', substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1, 9-substituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, Substituted or unsubstituted pyrazines, substituted or unsubstituted pyridazines, substituted or unsubstituted triazines, substituted or unsubstituted oxazoles, substituted or unsubstituted benzoxazoles, substituted or unsubstituted thiazoles, substituted or unsubstituted benzothiazoles, substituted or unsubstituted imidazoles, substituted or unsubstituted benzimidazoles, ketones, carboxylic acids, esters, nitriles, isonitriles, sulfinyl, sulfonyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,

Each of which R, R _e And R is _f Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; 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' . More detailed information about pi-electron deficient electron withdrawing groups can be found in U.S. provisional application No. 63/417,746 filed on day 10, 2022 and U.S. provisional application No. 63/481,143 filed on day 23, 2023, incorporated herein by reference.

In some embodiments, at least one R ^B A group comprising a member selected from the group consisting of: halogen, nitrile, fully fluorinated alkyl and partially fluorinated alkyl. In some embodiments, at least one R ^B Selected from the group consisting of: f, performing the process; CN, CF ₃ Cycloalkyl and CH ₂ CF ₃ 。

In some embodiments, a cyclic group is includedOr at least one R of electron withdrawing groups ^B A distal ring bonded to the fused ring structure of part B. As used herein, "distal" refers to the ring (or rings) furthest from the metal M.

In some embodiments, at least one R ^A Not hydrogen or deuterium. In some embodiments, at least one R ^A Is a partially or fully deuterated alkyl group.

In some embodiments, at least two R ^A Not hydrogen or deuterium. In some embodiments, at least two R ^A Each independently is a partially or fully deuterated alkyl group.

In some embodiments, two adjacent R' s ^A Or R is ^B May be joined to form a loop. In some embodiments, two adjacent R' s ^A Or R is ^B May be joined to form a 5-or 6-membered carbocyclic or heterocyclic aromatic ring. In some embodiments, two adjacent R' s ^A Or R is ^B May be joined to form a 5-or 6-membered carbocyclic or heterocyclic non-aromatic ring. In some embodiments, two adjacent R' s ^A Or R is ^B May be joined to form a ring selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole.

In some embodiments, the metal M is selected from the group consisting of: ir, os, rh, re, ru, pt, pd, cu, ag and Au. In some embodiments, the metal M is Ir. In some embodiments, the metal M is Pt or Pd.

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

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wherein:

Y ₁ 、Y ₂ 、Y ₃ 、Y ₄ 、Y ₅ 、Y ₆ 、Y ₇ 、Y ₈ 、Y ₉ 、Y ₁₀ 、Y ₁₁ 、Y ₁₂ 、Y ₁₃ 、Y ₁₄ 、Y ₁₅ and Y ₁₆ Is independently C or N;

each X is independently O, S, CR ₂ 、SiR ₂ Or NR;

R ^B1 represents a single substitution to the maximum possible number of substitutions, or no substitution;

each R and R ^B1 Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein;

at least one R ^B1 Comprising cyclic or electron withdrawing groups; and is also provided with

Two adjacent R ^B1 May be joined to form a loop.

In some embodiments, one R ^B1 An electron withdrawing group selected from the group consisting of the structures of list 1 as defined herein.

In some embodiments, one R ^B1 Is a 5-or 6-membered carbocyclic ringA heterocyclic aromatic ring. In some embodiments, one R ^B1 Is a 5-or 6-membered carbocyclic or heterocyclic non-aromatic ring. In some embodiments, one R ^B1 Selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole.

In some embodiments, ligand L _A Selected from the group consisting of the structures of the following list 3:

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wherein:

each X is independently O, S, CR or NR;

at least one R ^B1 Comprising cyclic or electron withdrawing groups; and any two R _A And R is ^B1 May be joined to form a loop.

In some embodiments, ligand L _A Selected from the group consisting of L _Ai -(R ⁿ )(R ^m )(E ^o )(W ^t ) A group consisting of, wherein i is an integer from 1 to 152, n and m are each independently an integer from 1 to 70, o is an integer from 1 to 125, and t is an integer from 1 to 16; wherein L is _A1 - (R1) (R1) (E1) (W1) to L _A152 The structure of- (R70) (R70) (E125) (W16) is as follows

Definition in table 4:

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wherein E1 to E125 have the structure defined in the following table 5:

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wherein W1 to W16 have the structure defined in the following table 6:

and wherein R1 to R70 have the structure defined in the following table 7:

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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 is a bidentate ligand; and wherein p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; and p+q+r is the oxidation state of 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 Ir (L _A ) ₃ Ir (L) _A )(L _Bk ) ₂ Ir (L) _Ai -(R ⁿ )(R ^m )(E ^o )(W ^t ))(L _B ) ₂ Ir (L) _A ) ₂ (L _Bk ) Ir (L) _Ai -(R ⁿ )(R ^m )(E ^o )(W ^t )) ₂ (L _B ) 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 Ligands as defined herein for formula I; l (L) _Bk Defined herein; and L is _Cj-I And L _Cj-II Each is defined herein. In some embodiments, the compound may have the formula Ir (L _Ai -(R ⁿ )(R ^m )(E ^o )(W ^t )) ₃ 、Ir(L _Ai -(R ⁿ )(R ^m )(E ^o )(W ^t )(L _Bk ) ₂ 、Ir(L _Ai -(R ⁿ )(R ^m )(E ^o )(W ^t )) ₂ (L _Bk )、Ir(L _Ai -(R ⁿ )(R ^m )(E ^o )(W ^t )) ₂ (L _Cj-I )、Ir(L _Ai -(R ⁿ )(R ^m )(E ^o )(W ^t )) ₂ (L _Cj-II ) Or Ir (L) _Ai -(R ⁿ )(R ^m )(E ^o )(W ^t ))(L _Bk )(L _Cj-II ) Wherein all variables are the same as previously defined.

In some embodiments, the compound has 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 some such embodiments, L _A And L _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 8:

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wherein 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 ；

Wherein R is _e And R is _f May 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 substitution to the maximum possible number of 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 as 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 embodiments, L _B And L _C Each independently selected from the group consisting of the structures of the following list 9:

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wherein R is _a '、R _b '、R _c '、R _d ' and R _e ' each independently represents zero substitution, mono substitution, or up to the maximum allowed substitution of its associated ring;

wherein R is _a '、R _b '、R _c '、R _d ' and R _e ' each independently is hydrogen or a substituent selected from the group consisting of the general substituents as defined herein; and is also provided with

Wherein R is _a1 、R _b1 、R _c1 、R _a '、R _b '、R _c '、R _d ' and R _e Two of the' may be fused or joined to form a ring or to form a multidentate ligand.

In some embodiments, the compound has a formula selected from the group consisting of: ir (L) _A ) ₃ Ir (L) _A )(L _Bk ) ₂ Ir (L) _A ) ₂ (L _Bk ) Ir (L) _A ) ₂ (L _Cj-I ) And Ir (L) _A ) ₂ (L _Cj-II )，

Wherein each L _A Is selected from any L described herein _A ；

Wherein k is an integer from 1 to 473;

wherein j is an integer from 1 to 1416;

wherein each L _Bk Having the structure defined in the following list 10:

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wherein each L _Cj-I With the basisIs of a structure of (2); and is also provided with

Each L _Cj-II With the basisWherein 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 11:

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wherein R is ^D1 To R ^D246 Having the structure defined in the following table 12:

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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 compound is selected from the group consisting of only compounds having L _Cj-I Or L _Cj-II A group consisting of those compounds of a ligand corresponding to R ²⁰¹ And R is ²⁰² 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 compound is selected from the group consisting of only compounds having L _Cj-I Or L _Cj-II A group consisting of those compounds of a ligand corresponding to R ²⁰¹ And R is ²⁰² 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 compound is selected from the group consisting of only compounds having the following L _Cj-I Those compounds of one of the ligand structures:

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

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wherein the method comprises the steps of

R ^10a 、R ^20a 、R ^30a 、R ^40a And R is ^50a Each of which independently represents a single substitution, up to a maximum substitution, or no substitution;

R ^10a 、R ^20a 、R ^30a 、R ^40a 、R ^50a and R is ⁹⁹ Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with

At least one R ^10a Or R is ^50a Comprising cyclic or electron withdrawing groups; and is also provided with

Two adjacent R ^10a 、R ^20a 、R ^30a 、R ^40a 、R ^50a And R is ⁹⁹ Optionally 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 13:

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in some embodiments, the compound has the formulaIn formula III:

M ¹ is 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 ³ and Z ⁴ Each independently is C or N;

K ¹ 、K ² 、K ³ and K ⁴ Each independently selected from the group consisting of a direct bond, O and S, wherein the K ¹ 、K ² 、K ³ And K ⁴ 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;

L ¹ and L ² At least one of which is present;

R ^E and R is ^F Each independently represents zero for its associated ringSubstitution, monosubstituted or up to a maximum allowable number of substitutions;

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

When chemically feasible, two adjacent 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, both moieties E and F are 6 membered aromatic rings.

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

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

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

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

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

In some embodiments, K ¹ 、K ² 、K ³ And K ⁴ Are direct keys.

In some embodiments, K ¹ 、K ² 、K ³ And K ⁴ One of which is O.

In some embodiments, the compound may be 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 structures shown in table 14 below:

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Wherein L is _y Selected from the group consisting of the structures shown in the following table 15:

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wherein Y is ₁ 、Y ₂ 、Y ₃ 、Y ₄ 、Y ₅ 、Y ₆ 、Y ₇ 、Y ₈ 、Y ₉ And Y ₁₀ Is independently C or N;

wherein R is ^A 、R ^B 、R ^E And R is ^F Independently monosubstituted up to a maximum allowable substitution or unsubstituted;

wherein each R is ^B Independently selected from the group consisting of the structures of list 15A, list 5 and list 6;

wherein at least one R ^B An electron withdrawing group comprising a cyclic group of list 6 or list 5;

wherein each R is ^A 、R ^E 、R ^F 、R ^X And R is ^Y Independently selected from the list consisting of the structures of the following list 15A:Me、iPr、tBu、CD ₃ 、/>/>

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in some embodiments, each R ^B Selected from the group consisting of the structures of list 5, list 6 and list 7 as defined herein. In some embodiments, at least one R ^B Comprising a cyclic group selected from the group consisting of W1 to W16 (list 6 defined herein) or an electron withdrawing group selected from the group consisting of E1 to E125 (list 5 defined herein).

wherein ligand L _A' Selected from the group consisting of L _A'i - (Rs) (Rt) (Vv), wherein i is an integer from 1 to 48, and s and t are each independently an integer from 1 to 70, and v is an integer from 1 to 44; wherein L is _A'1 - (R1) (R1) (V1) to L _A48 - (R70) (V44) is defined by the structure in the following list 16:

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wherein ligand L _y Selected from the group consisting of L _y j- (Rs) (Rt) (Ru), where j is an integer from 1 to 62, and s, t, and u are each independently integers from 1 to 70; wherein L is _y 1- (R1) (R1) (R1) to L _y 62- (R70) is defined by the structure in the following list 17:

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wherein for the position at L _A' Each occurrence of (1) and at L _y Each of s, t and u is independently an integer from 1 to 70, wherein R1 to R70 have the structure defined in table 7.

In some embodiments, the compound may be selected from the group consisting of the compounds of the following list 18:

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in some embodiments, the first ligand having formula I described hereinL _A The compound of (c) 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, deuterated percentages have their ordinary meaning and include the percentage of possible hydrogen atoms (e.g., the position of hydrogen, deuterium, or halogen) replaced by deuterium atoms.

In the presence of a compound having the formula M (L _A ) _p (L _B ) _q (L _C ) _r In some embodiments of the heteroleptic compounds of (2), ligand L _A Having a first substituent R ^I Wherein the first substituent R ^I a-I at ligand L _A Is furthest from the metal M among all atoms of (a). In addition, ligand L _B Having a second substituent R if present ^II Wherein the second substituent R ^II a-II at ligand L _B Is furthest from the metal M among all atoms of (a). In addition, ligand L _C Having a third substituent R if present ^III Wherein the third substituent R ^III The first atom a-III in the ligand L _C Is furthest from the metal M among all atoms of (a).

In such heteroleptic compounds, the vector V can be defined _D1 、V _D2 And V _D3 It is defined as follows. V (V) _D1 Represents the direction from the metal M to the first atom a-I, and the vector V _D1 Having a substituent R representing a metal M and a first substituent R ^I A value D of the linear distance between the first atoms a-I ¹ 。V _D2 Represents the direction from the metal M to the first atom a-II and the vector V _D2 Having a substituent R representing a metal M and a second substituent R ^II A value D of the linear distance between the first atoms a-II ² 。V _D3 Represents the direction from the metal M to the first atom a-III, and the vector V _D3 Having a substituent R representing a metal M and a third substituent R ^III A value D of the linear distance between the first atoms a-III ³ 。

In such heteroleptic compounds, spheres are defined having a radius r centered at the metal M and the radius r being the allowed sphere Not substituents R in the enclosing compounds ^I 、R ^II And R is ^III A minimum radius of all atoms of a portion of (a); and wherein D ¹ 、D ² And D ³ At least one of which is larger than the radius r by at leastIn some embodiments, D ¹ 、D ² And D ³ At least 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6 or +.>

In some embodiments of such heteroleptic compounds, the compound has a transition dipole moment axis and defines a transition dipole moment axis and a vector V _D1 、V _D2 And V _D3 Angle between the transition dipole moment axis and vector V _D1 、V _D2 And V _D3 At least one angle therebetween is less than 40 °. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least one angle therebetween is less than 30 °. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least one angle therebetween is less than 20. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least one angle therebetween is less than 15 °. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least one angle therebetween is less than 10 °. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least two angles therebetween being less than 20. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least two angles therebetween being less than 15. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 At least two angles therebetween being less than 10.

In some embodiments of the present invention, in some embodiments,transition dipole moment axis and vector V _D1 、V _D2 And V _D3 All three angles in between are less than 20 °. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 All three angles in between are less than 15 °. In some embodiments, the transition dipole moment axis is aligned with vector V _D1 、V _D2 And V _D3 All three angles in between are less than 10 °.

In some embodiments of such heteroleptic compounds, the compounds have a Vertical Dipole Ratio (VDR) of 0.33 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.30 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.25 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.20 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.15 or less.

The meaning of the term transition dipole moment axis of a compound and the perpendicular dipole ratio of the compound will be readily understood by those of ordinary skill in the art. However, the meaning of these terms can be found in U.S. patent No. 10,672,997, the disclosure of which is incorporated herein by reference in its entirety. In U.S. patent No. 10,672,997, the Horizontal Dipole Ratio (HDR) of a compound is discussed, rather than VDR. However, one skilled in the art will readily appreciate that vdr=1-HDR.

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 disclosed in the above compound portion 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 having formula I as described herein _A Is a compound of (a).

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 emissive layer includes one or more quantum dots.

In some embodiments, the organic layer may further comprise a host, wherein the host comprises a benzofused thiophene or benzofused furan comprising triphenylene, 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 And Ar is a group 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, 5λ ² Benzo [ d ]]Benzo [4,5 ]]Imidazo [3,2-a]Imidazole, 5, 9-dioxa-13 b-boronaphtho [3,2,1-de]Anthracene, triazine, boron, silane, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ ² Benzo [ d ]]Benzo [4,5 ]]Imidazo [3,2-a]Imidazole and aza- (5, 9-dioxa-13 b-boronaphtho [3,2, 1-de)]Anthracene).

In some embodiments, the subject may be selected from the group of subjects 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 comprise 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 Is a compound of (a).

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 having formula I as described herein _A Is a compound of (a).

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 substrate-anode combination is disclosed in U.S. patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is 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), 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 that contains one or more light sources and/or one or more of some 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 phosphor-photosensitizing agent 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 derivatives, e.g. 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:

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, benzofuranopyridine, furodipyrazine Pyridine, benzothienopyridine, 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, 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, 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, the following stepsY 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 a metal; (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, benzofuranopyridine, furanodizine Pyridine, benzothienopyridine, 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 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 examples of the invention

1-bromo-4-chloro-2-iodobenzene (1) (50 g,158 mmol), copper (I) iodide (0.750 g,3.94 mmol) and bis (triphenylphosphine) palladium (II) chloride (2.76 g,3.94 mmol) were combined and suspended in THF (315 ml) and triethylamine (132 ml,945 mmol). The flask was vacuum/backfilled N2 10 times (until boiling). Ethynyl trimethylsilane (17.02 g,173 mmol) was then added via syringe pump over the course of 75 minutes and the reaction stirred at room temperature for 18h. The reaction mixture changed from yellow to black over the course of 2 hours. The reaction was filtered through celite (10 g cartridge) and the filter was washed with THF (200 mL). The organics were diluted with diethyl ether (1L) and washed with brine (3×250 mL) before drying over MgSO 4. Filtration and subsequent concentration in vacuo afforded a deep orange oil (47 g). The oil was suspended in isohexane (200 mL), filtered through a plug of silica (about 20 g), and the plug was washed with additional isohexane (300 mL). Concentration in vacuo afforded an orange oil, which was dissolved in isohexane (200 mL) and added with activated carbon (1 spatula). The suspension was filtered through a plug of silica (20 g) and washed with isohexane (200 mL), followed by removal of the solvent in vacuo to give ((2-bromo-5-chlorophenyl) ethynyl) trimethylsilane (2) (45.6 g,155mmol,99% yield) as a yellow oil.

Dibenzo [ b, d ] furan-4-ylboronic acid (3) (34.5 g,163 mmol), tetrakis (triphenylphosphine) palladium (0) (8.96 g,7.75 mmol), sodium carbonate (49.3 g, 460 mmol), ((2-bromo-5-chlorophenyl) ethynyl) trimethylsilane (2) (44.6 g,155 mmol) and toluene (500 mL) were added to a 3-neck 2L flask equipped with a condenser. The vessel was vacuum/backfilled with nitrogen 3 times, followed by the addition of ethanol (125 mL) and water (125 mL). The reaction vessel was vacuum/backfilled with nitrogen 3 times (until the solvent boiled) and the reaction was sparged with nitrogen for 30 minutes. The reaction mixture was heated to 80 ℃ for 22h. The reaction was then cooled to room temperature and diluted with ethyl acetate (500 mL). Followed by washing with brine (3X 250 mL). The organics were dried over MgSO4 and concentrated in vacuo to give a brown oil suspended in isohexane. The resulting brown solid was filtered off and discarded. The remaining deep orange oil was purified using a silica plug eluting with pure isohexane. The fractions were combined and concentrated in vacuo to give ((5-chloro-2- (dibenzo [ b, d ] furan-4-yl) phenyl) ethynyl) trimethylsilane (4) (52.75 g,139mmol,90% yield) as an orange oil which slowly crystallized as a solid.

((5-chloro-2- (dibenzo [ b, d ] furan-4-yl) phenyl) ethynyl) trimethylsilane (4) (46.92 g,125 mmol) was dissolved in MeOH (600 mL) and DCM (150 mL) and potassium carbonate (17.29 g,125 mmol) were added in one portion. The reaction was stirred at 25 ℃ for 17h, a thick white precipitate formed over time. The solid was collected by filtration and washed with MeOH (200 mL). The solid was then dissolved in DCM (1L) and washed with water (250 mL) and saturated brine (250 mL aqueous solution), followed by passage through a phase separator cartridge and concentration in vacuo afforded 4- (4-chloro-2-ethynylphenyl) dibenzo [ b, d ] furan (5) (33.2 g,107mmol,86% yield) as a pale orange solid.

4- (4-chloro-2-ethynylphenyl) dibenzo [ b, d ] furan (5) (34.9 g,115 mmol) was dissolved in toluene (1200 mL) and the solution was bubbled with nitrogen for 20min, followed by the addition of gold (III) chloride (7.00 g,23.06 mmol) in one portion. The suspension was again bubbled with nitrogen for 5 minutes, then heated to 100 ℃ and stirred at this temperature for 24 hours. The brown reaction was filtered hot through celite and then left to stand overnight at room temperature. The light brown crystals formed were collected by filtration and washed with isohexane (about 200 mL). The filtrate was concentrated in vacuo to give a dark brown solid. The crystals were dissolved in hot DCM (2L) and then stirred on silica (4 big spatula) and charcoal (1 big spatula) at 40 ℃ for 30 minutes. The suspension was filtered through celite, and silica (4 x spatula) and charcoal (1 x spatula) were added to the resulting yellow filtrate and stirred at 40 ℃ for an additional 30min. Filtration through celite afforded a pale yellow solution which was concentrated in vacuo to afford 13g of a yellow solid. The filtrate was dissolved in hot toluene (550 mL) and allowed to crystallize overnight at room temperature. The resulting light brown crystals were collected by filtration and washed with isohexane, and the filtrate was concentrated in vacuo to give a dark brown solid. The crystals were dissolved in warm DCM (1.5 l,40 ℃) and stirred on silica (3 x spatula) and charcoal (1 x spatula) for 30 minutes. Filtration through celite afforded a yellow solution to which silica (3 x spatula) and charcoal (1 x spatula) were added and stirred at 40 ℃ for 30 minutes. Filtration through celite afforded a pale yellow solution which was combined with 13g of the previous isolation and concentrated in vacuo to afford 22.8g of a yellow solid. The second filtrate was dissolved in hot toluene (250 mL) and allowed to crystallize overnight at room temperature. The resulting light brown crystals were collected by filtration and washed with isohexane. The crystals were dissolved in warm DCM (500 ml,40 ℃) and stirred on silica (3 x spatula) and charcoal (1 x spatula) for 30 minutes. Filtration through celite afforded a yellow solution to which silica (3 x spatula) and charcoal (1 x spatula) were added and stirred at 40 ℃ for 30min. Filtration through celite afforded a pale yellow solution which was combined with the aforementioned 22g batch and concentrated in vacuo to afford 24.8g of a yellow solid. This solid was dissolved in hot toluene (450 mL) and left to stand at room temperature for 64h. The resulting crystals were collected by filtration and washed with isohexane (250 mL) followed by drying under vacuum at 50 ℃ for 90min. Pale yellow fine crystals 21.16g were obtained, which were then dissolved in warm DCM (1.5 l,40 ℃) and stirred on silica (3 x spatula) and charcoal (1 x spatula) for 30min. Filtration through celite gave a pale yellow solution, to which silica (3 x spatula) and charcoal (1 x spatula) were added and stirred at 40 ℃ for 30min. Filtration through celite afforded a pale yellow solution which was concentrated in vacuo to afford 19.01g (62.8 mmol, 54.5%) of a pale yellow fluffy solid.

3-chlorophenanthro [4,3-b ] benzofuran (6) (3.0 g,9.91 mmol) and phenylboronic acid (2.4 g,2 eq.) are suspended in 75mL of toluene and 20mL of water. The palladium G2 XPhos catalyst (2 mol%) and XPhos ligand (5 mol%) were added in one portion. The reaction mixture was degassed and heated to 100 ℃ for 5h, then cooled to room temperature and evaporated. The residue was subjected to silica gel column chromatography eluting with heptane/DCM 1/1 (v/v) to provide 3-phenylphenanthro [4,3-b ] benzofuran (3.24 g,90% yield) as a white solid.

3-Phenanthro [4,3-b ] benzofuran (7) (7.2 g,20.91 mmol) was dissolved in 150mL dry THF under nitrogen and cooled in an acetone/dry ice bath. A solution of sec-butyllithium in hexane (30 ml,41.8 mmol) was added via syringe and the reaction mixture stirred for 45min followed by dropwise addition of 2-isopropoxy-4, 5-tetramethyl-1, 3, 2-dioxaborolan (7.78 g,41.8 mmol) via syringe. The reaction mixture was allowed to warm to room temperature and stirred for 12h. It was quenched with 10% aqueous ammonium chloride, extracted with ethyl acetate, filtered and evaporated. The residue was subjected to column chromatography on a silica gel column eluting with a heptane/ethyl acetate gradient mixture to provide 4, 5-tetramethyl-2- (3-phenylphenanthro [4,3-b ] benzofuran-12-yl) -1,3, 2-dioxaborolan (4.9 g,50% yield) as a white solid.

4, 5-tetramethyl-2- (3-phenylphenanthro [4,3-b ] benzofuran-12-yl) -1,3, 2-dioxaborolan (8) (3.2 g,6.80 mmol) and 2-chloro-4- (2, 2-dimethylpropyl-1, 1-d 2) -5- (methyl-d 3) pyridine were suspended in DME (150 mL)/water (30 mL) and Pd catalyst (160 mg,2 mol%) and potassium carbonate (1.88 g,2 eq) were added. The reaction mixture was degassed and heated to 80 ℃ for 16h. The reaction mixture was cooled, diluted with ethyl acetate, washed with water, filtered and evaporated. The residue was subjected to silica gel column chromatography eluting with a gradient mixture of heptane/ethyl acetate to provide 4- (2, 2-dimethylpropyl-1, 1-d 2) -5- (methyl-d 3) -2- (3-phenylphenanthro [4,3-b ] benzofuran-12-yl) pyridine (9) as a white solid (3.12 g,90% yield).

Iridium triflate complex (1.8 g) and ligand (1.8 g,1.75 eq.) were suspended in 40mL DMF/2-ethoxyethanol 1/1 mixture. The reaction mixture was degassed and heated to 100 ℃ for 120h. The material was dissolved in ethyl acetate, washed with brine and evaporated. The residue was subjected to column chromatography on a silica gel column eluting with a toluene/heptane/DCM 3/1/1 mixture. The pure fractions were combined, evaporated and crystallized from toluene/ethanol to give 920mg of pure product as yellow needles.

Synthesis of comparative examples

The synthesis of the comparative example can be found in US20190280219, which is incorporated herein by reference in its entirety.

Device instance

Through high vacuum<10 ^-7 Tray) thermal evaporation was used to make all example devices. 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 (H) ₂ O and O ₂ <1 ppm) of a glass lid sealed with an epoxy resin, wherein a desiccant is incorporated inside the package. The organic stack of the device example consisted of the following in order starting from the ITO surface: />LG101 (from LG chemistry) as a Hole Injection Layer (HIL); />As a Hole Transport Layer (HTL); thickness of-> An emissive layer (EML); />As an Electron Blocking Layer (EBL); the emissive layer contains an H-host (H1) E-host (H2) and 5 wt% green emitter in a ratio of 6:4; />Is doped with 35% ETM as ETL. The device structure is shown in table 1. The chemical structure of the device material is shown below.

TABLE 1 device layer materials and thicknesses

The device was tested after fabrication to measure EL and JVL. For this purpose, samples10mA/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. The scanning voltage is 0 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, LE, EQE, and PE of the examples of the invention are reported as relative numbers normalized to the results of the comparative examples.

TABLE 2 device Performance results

Table 2 provides a summary of the performance of the electroluminescent devices of the materials. The present examples demonstrate higher efficiency than the comparative examples. Furthermore, inventive example 1 exhibited better LT, LE and PE than comparative example 1. 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 is unexpected. All the results indicate the importance of the use of the compounds according to the invention in organic light-emitting diodes (OLEDs).

Claims

1. A compound comprising formula I Is a first ligand L of (2) _A Wherein:

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

k is a direct bond, S or O;

Z ¹ and Z ² Each of which is independentlyIs C or N;

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

any two R ^A Or R is ^B May be joined or fused to form a ring;

at least one R ^B Comprising cyclic or electron withdrawing groups;

L _A coordination with metal M;

2. The compound of claim 1, wherein part a is 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, phenanthridine, fluorene, and aza-fluorene; and/or

Wherein part B comprises at least one compound of formula IIIs a ring of (2);

wherein Y is selected from the group consisting of: BR ', BR ' R ", NR ', PR ', P (O) R ', 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"、

Alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof;

wherein each R' or R "is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, boron, selenium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and/or

Wherein part B comprises at least four six-membered rings; and/or wherein Z ¹ Is N and Z ² Is C, or wherein Z ¹ Is C and Z ² Is N; and/or wherein metal M is selected from the group consisting of: ir, os, rh, re, ru, pt, pd, cu, ag and Au.

3. The compound of claim 1, wherein at least one R ^B Comprising at least one monocyclic or fused polycyclic group; and/or

Wherein at least one R ^B An electron withdrawing group selected from the group consisting of: 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) ₃ 、(R) ₂ CCN、(R) ₂ CCF ₃ 、CNC(CF ₃ ) ₂ BRR', substituted or unsubstituted dibenzoborolan, 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 alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,

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 GeReRf', wherein

Each R, R _e And R is _f Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, and,Sulfinyl, sulfonyl, phosphinyl, boron, seleno, and combinations thereof, and 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' 。

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

wherein:

Y ₁ 、Y ₂ 、Y ₃ 、Y ₄ 、Y ₅ 、Y ₆ 、Y ₇ 、Y ₈ 、Y ₉ 、Y ₁₀ 、Y ₁₁ 、Y ₁₂ 、Y ₁₃ 、Y ₁₄ 、Y ₁₅ and

Y ₁₆ is independently C or N;

each R and R ^B1 Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, boron, selenium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof;

Two adjacent R ^B1 May be joined to form a loop.

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

/>

wherein:

Two adjacent R ^B1 May be joined to form a loop.

6. The compound of claim 1, wherein the ligand L _A Selected from the group consisting of L _Ai -(R ⁿ )(R ^m )(E ^o )(W ^t ) A group consisting of, wherein i is an integer from 1 to 152, n and m are each independently an integer from 1 to 70, o is an integer from 1 to 125, and t is an integer from 1 to 16; wherein L is _A1 - (R1) (R1) (E1) (W1) to L _A152 -(R70)(R70) (E125) (W16) is defined as follows:

/>

Wherein E1 through E125 have the following structure:

/>

wherein W1 to W16 have the following structure:

and wherein R1 to R70 have the following structure:

/>

7. the compound of claim 1, wherein the compound has the formula (la)

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

8. The compound of claim 7, 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 Are different from each other; wherein the compound has 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.

9. The compound of claim 7, 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 ' is a direct bond or is selected from the group consisting of: NR (NR) _e 、PR _e O, S and Se;

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

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 May be fused or joined to form a ring;

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

Each R _a1 、R _b1 、R _c1 、R _d1 、R _a 、R _b 、R _c 、R _d 、R _e And R is _f Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, boron, selenium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and is also provided with

R _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.

10. The compound of claim 7, wherein the compound has a formula selected from the group consisting of: ir (L) _A ) ₃ Ir (L) _A )(L _Bk ) ₂ Ir (L) _A ) ₂ (L _Bk ) Ir (L) _A ) ₂ (L _Cj-I ) And Ir (L) _A ) ₂ (L _Cj-II ) Wherein each L _A Is defined according to claim 1;

wherein k is an integer from 1 to 473;

wherein j is an integer from 1 to 1416;

wherein each L _B1 To L _B473 The structure is as follows:

/>

wherein each L _Cj-I With the basisIs of a structure of (2); and->

Each L _Cj-II With the basisWherein for L _Cj-I And L _Cj-II Each L of (3) _Cj ，R ²⁰¹ And R is ²⁰² The definition is as follows:

/>

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

/>

11. the compound of claim 1, wherein the first ligand L comprising formula I _A The compound of (2) is selected fromA group consisting of:

/>

wherein the method comprises the steps of

R ^10a 、R ^20a 、R ^30a 、R ^40a And R is ^50a Each of which independently represents a single substitution up to a maximum substitution,

or unsubstituted;

R ^10a 、R ^20a 、R ^30a 、R ^40a 、R ^50a and R is ⁹⁹ Is independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanium, boron, selenium, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and is also provided with

Two adjacent R ^10a 、R ^20a 、R ^30a 、R ^40a 、R ^50a And R is ⁹⁹ Optionally joined or fused to form a ring.

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

/>

13. the compound of claim 7, wherein the compound has formula III:

wherein:

M ¹ is Pd or Pt;

Z ³ and Z ⁴ Each independently is C or N;

K ¹ 、K ² 、K ³ and K ⁴ Each independently selected from the group consisting of a direct bond, O and S, wherein the

K ¹ 、K ² 、K ³ And K ⁴ 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;

L ¹ and L ² At least one of which is present;

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

each R, R', R ^E And R is ^F Independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof; and is also provided with

14. An organic light emitting device, comprising:

an anode;

a cathode; and

an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a polymer of formula IIs a first ligand L of (2) _A Wherein:

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

K is a direct bond, S or O;

Z ¹ and Z ² Is independently C or N;

any two R ^A Or R is ^B May be joined or fused to form a ring;

at least one R ^B Comprising cyclic or electron withdrawing groups;

L _A coordination with metal M;

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

an anode;

a cathode; and

an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a polymer of formula I Is a first ligand L of (2) _A Wherein:

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

k is a direct bond, S or O;

Z ¹ and Z ² Is independently C or N;

any two R ^A Or R is ^B May be joined or fused to form a ring;

at least one R ^B Comprising cyclic or electron withdrawing groups;

L _A coordination with metal M;

The ligand L _A Optionally linked to other ligands to form tridentates, tetradentates, pentadentates Or a hexadentate ligand.