CN112341498B

CN112341498B - Organic electroluminescent material and device

Info

Publication number: CN112341498B
Application number: CN202010788139.2A
Authority: CN
Inventors: M·C·马克尼斯; 斯科特·比尔斯; 陈小凡; 格扎·西盖蒂; 约瑟夫·A·马克尔; 贾森·布鲁克斯
Original assignee: Universal Display Corp
Current assignee: Universal Display Corp
Priority date: 2019-08-08
Filing date: 2020-08-07
Publication date: 2024-09-10
Anticipated expiration: 2040-08-07
Also published as: CN112341498A

Abstract

The present invention relates to organic electroluminescent materials and devices. There is provided a compound of formula Ir (L _A)_x(L_B)_y(L_C)_z wherein L _A has

Description

Organic electroluminescent material and device

Cross reference to related applications

The present application claims priority from U.S. c. ≡119 (e) to U.S. provisional application No. 62/884,329 filed 8/2019, the entire contents of which are incorporated herein by reference.

Technical Field

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

Background

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

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

One application of phosphorescent emissive molecules is in full color displays. Industry standards for such displays require pixels adapted to emit a particular color (referred to as a "saturated" color). In particular, these standards require saturated red, green and blue pixels. Or 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

Iridium complexes having a clasping (strapped) carbene ligand are provided. The iridium complex comprises an N-heterocyclic carbene (NHC) ligand containing a group that binds the NHC to a cyclometallated benzene ring. When iridium complexes are used as emitter dopants in OLEDs, these ligands provide complexes that exhibit improved device lifetime compared to comparative complexes where the NHC is not attached to a cyclometallated phenyl group.

In one aspect, the present disclosure provides a compound of formula Ir (L _A)_x(L_B)_y(L_C)_z, wherein L _A has

I is a kind ofOr formula II

Wherein: x ¹ to X ⁹ are each independently C or N; r ^A、R^B and R ^C each independently represent zero substitution, mono substitution or up to the maximum allowed substitution of their associated rings; y is an atomic linker and Z is a diatomic linker; the linking atoms in Y and Z are each independently selected from the group consisting of: BR ', NR ', PR ', O, S, CR ' R ' and SiR ' R '; t ¹ and T ² are C; r, R', R ", R ¹、R²、R^A、R^B and R ^C are each independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; x is 1 or 2; y and z are each independently 0, 1 or 2; and x+y +z=3; wherein if L _A has formula I, then L _B and L _C are each independently selected from the group consisting of:

Wherein: y ¹ to Y ¹³ are each independently selected from the group consisting of: c and N; y' is selected from the group consisting of ：BR_e、NR_e、PR_e、O、S、Se、C＝O、S＝O、SO₂、CR_eR_f、SiR_eR_f and GeR _eR_f;R_e and R _f may be fused or joined to form a ring; r _a、R_b、R_c、R_d、R_g、R_h and R _i each independently represent zero substitution, mono substitution or up to the maximum allowed substitution of their associated rings; and R _a、R_b、R_c、R_d、R_e、R_f、R_g、R_h and R _i are each independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; x is selected from the group consisting of: B. al, ga and In; either of L _A、L_B and L _C may be joined together to form a tetradentate or hexadentate ligand; if L _A is of formula II, then L _B and L _C are each a bidentate monoanionic ligand; and the two substituents may be joined or fused together to form a ring.

In another aspect, the present disclosure provides a formulation of a compound of the present disclosure.

In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound of the present disclosure.

In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a compound of the present disclosure.

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 (a less negative (LESS NEGATIVE) IP). 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) group.

The term "ether" refers to the-OR _s group.

The term "thio" or "thioether" is used interchangeably and refers to the-SR _s group.

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

The term "sulfonyl" refers to the-SO ₂-R_s group.

The term "phosphino" refers to-P (R _s)₃ groups, where each R _s may be the same or different).

The term "silane group" refers to-Si (R _s)₃ groups, where each R _s may be the same or different).

The term "oxyboronyl" refers to-B (R _s)₂ group or its lewis adduct (Lewis adduct) -B (R _s)₃ group), wherein R _s may be the same or different.

In each of the foregoing, R _s may be hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R _s is 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 is a preferred heteroatom. 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, oxazole, 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 pyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-azaborane, 1, 3-azaborane, 1, 4-azaborane, borazine, and aza analogues thereof are preferred. 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, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, oxyboronyl, 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, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, oxyboronyl, 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, oxyboroyl, 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 represents a single substitution, then one R ¹ must not be H (i.e., a substitution). Similarly, when R ¹ represents a di-substitution, then both R ¹ must not be H. Similarly, when R ¹ represents zero or no substitution, R ¹ may be, for example, hydrogen of available valence of the ring atoms, such as carbon atoms of benzene and nitrogen atoms in pyrrole, or simply no for ring atoms having a fully saturated valence, 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. US2011/0037057 (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 (Tetrahedron) 2015,71,1425-30 and Azrote (Atzrodt) et al, german application chemistry (Angew. Chem. Int. Ed.) (review) 2007,46,7744-65, which is incorporated by reference in its entirety, describes the deuteration of methylene hydrogen in benzylamine and the efficient route to 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

I is a kind ofOr formula II

In some embodiments, L _A has formula I, and each of L _B and L _C is independently selected from the group consisting of:

Wherein R _a、R_b、R_c、R_d、R_e、R_f and R _g are as defined above.

In some embodiments, R, R', R ", R ¹、R²、R^A、R^B, and R ^C are each independently hydrogen or a substituent selected from the group consisting of preferred general substituents defined herein.

In some embodiments, Y is selected from the group consisting of: o, NR ', CR ' R ' and SiR ' R '.

In some embodiments, each of X ¹ to X ⁶ is C.

In some embodiments, R is aryl, heteroaryl, alkyl, or cycloalkyl.

In some embodiments, each R ^A is H.

In some embodiments, each R ^B is H.

In some embodiments, Y is selected from the group consisting of structures in the following Y list:

And wherein Z is selected from the group consisting of structures in the following list of Z:

In some embodiments of the compounds, the linking atoms in Z are each CR 'R'. In some embodiments, R' and R "are each independently selected from the group consisting of: alkyl, cycloalkyl, aryl, and heteroaryl.

In some embodiments of the compounds, one of the two linking atoms in Z is SiR 'R "and the other is CR' R". In some embodiments, R' and R "are each independently selected from the group consisting of: alkyl, cycloalkyl, aryl, and heteroaryl.

In some embodiments of the compounds, one of the two linking atoms in Z is O or S and the other is CR 'R "or SiR' R". In some embodiments, R' and R "are each independently selected from the group consisting of: alkyl, cycloalkyl, aryl, and heteroaryl.

In some embodiments of the compound, R ¹ is selected from the group consisting of: alkyl, cycloalkyl, aryl, and heteroaryl.

In some embodiments, R ² is selected from the group consisting of: hydrogen, alkyl, cycloalkyl, aryl, and heteroaryl.

In some embodiments, X ⁷、X⁸ and X ⁹ are each C.

In some embodiments, each R ^C is H.

In some embodiments of compounds wherein Y is selected from the group consisting of Y list and Z is selected from the group consisting of Z list, ligand L _A has a structure according to formula I-1And is selected from the group consisting of: based on the numbering schemes L _A1-(y)(a)(i)(j)(k)(l)(m),L_A 1- (1) (3) (1) (1) (1) through L _A 1- (37) (14) (14) (14) (14), or

Ligand L _A has a structure according to formula II-1And is selected from the group consisting of: based on numbering schemes L _A2-(z)(a)(i)(j)(k),L_A 2- (1) (3) (1) (1) (1) through L _A 2- (206) (14) (14) (14) (14);

Wherein R ^A has the structure of R ^Aa, R ^I has the structure of R ^Ai, R ^J has the structure of R ^Aj, R ^K has the structure of R ^Ak, R ^L has the structure of R ^Al, and R ^M has the structure of R ^Am;

In formula I-1, Y has the structure of S ^y, and in formula II-1, Z has the structure of S' ^z;

y is an integer from 1 to 37, z is an integer from 1 to 206, a is an integer from 3 to 14, i, j, k, l and m are each independently an integer from 1 to 14; and

R ^A1 to R ^A14 have the structure defined below:

In some embodiments of the compounds, when L _A has formula II, L _B and L _C may each be independently selected from the group consisting of:

Wherein: y ¹ to Y ¹³ are each independently selected from the group consisting of: carbon and nitrogen; y' is selected from the group consisting of ：BR_e、NR_e、PR_e、O、S、Se、C＝O、S＝O、SO₂、CR_eR_f、SiR_eR_f and GeR _eR_f;R_e and R _f may be fused or joined to form a ring; r _a、R_b、R_c、R_d、R_g、R_h and R _i each independently represent zero substitution, mono substitution or up to the maximum allowed substitution of their associated rings; and R _a、R_b、R_c、R_d、R_e、R_f、R_g、R_h and R _i are each independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and X is selected from the group consisting of: B. al, ga and In; two adjacent substituents in R _a、R_b、R_c and R _d may be fused or joined to form a ring or to form a multidentate ligand.

In some embodiments wherein L _A is a compound of formula I-1 or formula II-1, the compounds are selected from the group consisting of ：Ir[(L_A1-(y)(a)(i)(j)(k)(l)(m)]₂(L_Bq)、Ir[(L_A1-(y)(a)(i)(j)(k)(l)(m)](L_Bq)₂、Ir[(L_A2-(z)(a)(i)(j)(k)]₂(L_Bq) and Ir [ (L _A2-(z)(a)(i)(j)(k)](L_Bq)₂) whose structures are as defined above, wherein y is an integer from 1 to 37, z is an integer from 1 to 206, a is an integer from 3 to 14, I, j, k, L and m are each independently an integer from 1 to 14, wherein q is an integer from 1 to 446, and wherein L _B1 to L _B446 have the structures:

In some embodiments wherein L _A is a compound of formula I-1 or formula II-1, the compound is selected from the group consisting of ：Ir[(L_A1-(y)(a)(i)(j)(k)(l)(m)]₂(L_Bq)、Ir[(L_A1-(y)(a)(i)(j)(k)(l)(m)](L_Bq)₂、Ir[(L_A2-(z)(a)(i)(j)(k)]₂(L_Bq) and Ir [ (L _A2-(z)(a)(i)(j)(k)](L_Bq)₂); wherein y is an integer from 1 to 37, z is an integer from 1 to 206, a is an integer from 3 to 14, I, j, k, L and m are each independently integers from 1 to 14, wherein q is an integer selected from the group consisting of 147, 148, 149, 150, 214, 216, 366, 375, 382, 397, 415, 422, 433 and 440.

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

C. OLED and device of the present disclosure

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

The OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound of formula Ir (L _A)_x(L_B)_y(L_C)_z, wherein L _A has

I is a kind ofOr formula IIWherein: x ¹ to X ⁹ are each independently C or N; r ^A、R^B and R ^C each independently represent zero substitution, mono substitution or up to the maximum allowed substitution of their associated rings; y is an atomic linker and Z is a diatomic linker; the linking atoms in Y and Z are each independently selected from the group consisting of: BR ', NR ', PR ', O, S, CR ' R ' and SiR ' R '; t ¹ and T ² are C; r, R', R ", R ¹、R²、R^A、R^B and R ^C are each independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; x is 1 or 2; y and z are each independently 0,1 or 2; and x+y +z=3; wherein if L _A has formula I, then L _B and L _C are each independently selected from the group consisting of:

Wherein: y ¹ to Y ¹³ are each independently selected from the group consisting of: c and N; y' is selected from the group consisting of ：BR_e、NR_e、PR_e、O、S、Se、C＝O、S＝O、SO₂、CR_eR_f、SiR_eR_f and GeR _eR_f;R_e and R _f may be fused or joined to form a ring; r _a、R_b、R_c、R_d、R_g、R_h and R _i each independently represent zero substitution, mono substitution or up to the maximum allowed substitution of their associated rings; and R _a、R_b、R_c、R_d、R_e、R_f、R_g、R_h and R _i are each independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; x is selected from the group consisting of: B. al, ga and In; either of L _A、L_B and L _C may be joined together to form a tetradentate or hexadentate ligand; if L _A is of formula II, then L _B and L _C are each a bidentate monoanionic ligand; and the two substituents may be joined or fused together to form a ring.

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

In some embodiments, the organic layer may further comprise a host, wherein the host comprises triphenylene comprising a benzo-fused thiophene or a benzo-fused furan, wherein any substituents in the host are non-fused substituents ：C_nH_2n+1、OC_nH_2n+1、OAr₁、N(C_nH_2n+1)₂、N(Ar₁)(Ar₂)、CH＝CH-C_nH_2n+1、C≡CC_nH_2n+1、Ar₁、Ar₁-Ar₂、C_nH_2n-Ar₁ or no substituents independently selected from the group consisting of, wherein n is 1 to 10; and wherein Ar ₁ and Ar ₂ are 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, 5, 9-dioxa-13 b-boranaphtho [3,2,1-de ] anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza- (5, 9-dioxa-13 b-boranaphtho [3,2,1-de ] anthracene).

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

and combinations thereof.

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

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 compound of formula Ir (L _A)_x(L_B)_y(L_C)_z, where L _A has the formula

I is a kind ofOr formula IIWherein: x ¹ to X ⁹ are each independently C or N; r ^A、R^B and R ^C each independently represent zero substitution, mono substitution or up to the maximum allowed substitution of their associated rings; y is an atomic linker and Z is a diatomic linker; the linking atoms in Y and Z are each independently selected from the group consisting of: BR ', NR ', PR ', O, S, CR ' R ' and SiR ' R '; t ¹ and T ² are C; r, R', R ", R ¹、R²、R^A、R^B and R ^C are each independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; x is 1 or 2; y and z are each independently 0, 1 or 2; and x+y +z=3; wherein if L _A has formula I, then L _B and L _C are each independently selected from the group consisting of:

In some embodiments of the emissive region, the compound may be an emissive dopant or a non-emissive dopant. In some embodiments, the emissive region further comprises a host, wherein the host contains at least one group selected from the group consisting of: metal complexes, triphenylenes, carbazoles, dibenzothiophenes, dibenzofurans, dibenzoselenophenes, aza-triphenylenes, aza-carbazoles, aza-dibenzothiophenes, aza-dibenzofurans, and aza-dibenzoselenophenes. In some embodiments, the subject is selected from the group consisting of the structures listed in the subject group defined herein.

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 compound of formula Ir (L _A)_x(L_B)_y(L_C)_z, wherein L _A has

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 (excimer) or an 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, volume 395, 151-154,1998 ("Baldo-I"); and Barduo et al, "Very high efficiency 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) ("Barduo-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 m-MTDATA doped with F ₄ -TCNQ at a molar ratio of 50:1, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of 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) (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 (supramolecule) (also referred to as supramolecules (supermolecule)). 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 the 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 ：EP01617493、EP01968131、EP2020694、EP2684932、US20050139810、US20070160905、US20090167167、US2010288362、WO06081780、WO2009003455、WO2009008277、WO2009011327、WO2014009310、US2007252140、US2015060804、US20150123047 and US2012146012 along with references disclosing those materials.

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 such as MoO _x; 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:

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

wherein k is an integer from 1 to 20; x ¹⁰¹ to X ¹⁰⁸ are C (including CH) or N; z ¹⁰¹ is NAr ¹, O or S; ar ¹ has 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-Y¹⁰²) is a bidentate ligand, Y ¹⁰¹ and Y ¹⁰² are independently selected from C, N, O, P and S; l ¹⁰¹ is a secondary ligand; k' is an integer value of 1 to the maximum number of ligands that can be attached to the metal; and k' +k "is the maximum number of ligands that can be attached to the metal.

In one aspect, (Y ¹⁰¹-Y¹⁰²) is a 2-phenylpyridine derivative. In another aspect, (Y ¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, met is selected from Ir, pt, os, and Zn. In another aspect, the metal complex has a minimum oxidation potential in solution of less than about 0.6V compared to Fc ⁺/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 below along with references disclosing those materials ：CN102702075、DE102012005215、EP01624500、EP01698613、EP01806334、EP01930964、EP01972613、EP01997799、EP02011790、EP02055700、EP02055701、EP1725079、EP2085382、EP2660300、EP650955、JP07-073529、JP2005112765、JP2007091719、JP2008021687、JP2014-009196、KR20110088898、KR20130077473、TW201139402、US06517957、US20020158242、US20030162053、US20050123751、US20060182993、US20060240279、US20070145888、US20070181874、US20070278938、US20080014464、US20080091025、US20080106190、US20080124572、US20080145707、US20080220265、US20080233434、US20080303417、US2008107919、US20090115320、US20090167161、US2009066235、US2011007385、US20110163302、US2011240968、US2011278551、US2012205642、US2013241401、US20140117329、US2014183517、US5061569、US5639914、WO05075451、WO07125714、WO08023550、WO08023759、WO2009145016、WO2010061824、WO2011075644、WO2012177006、WO2013018530、WO2013039073、WO2013087142、WO2013118812、WO2013120577、WO2013157367、WO2013175747、WO2014002873、WO2014015935、WO2014015937、WO2014030872、WO2014030921、WO2014034791、WO2014104514、WO2014157018.

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-Y¹⁰⁴) is a bidentate ligand, Y ¹⁰³ and Y ¹⁰⁴ are independently selected from C, N, O, P and S; 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-Y¹⁰⁴) is a carbene ligand.

In one aspect, the host compound contains at least one selected from the group consisting of: a group consisting of, for example, the following aromatic hydrocarbon cyclic compounds: benzene, biphenyl, triphenylene, tetramethylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furandipyridine, benzothiophenopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and a group 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 ¹⁰¹ is selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has a similar definition as Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20. X ¹⁰¹ to X ¹⁰⁸ are independently selected from C (including CH) or N. Z ¹⁰¹ and Z ¹⁰² are independently selected from NR ¹⁰¹, O or S.

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 ：EP2034538、EP2034538A、EP2757608、JP2007254297、KR20100079458、KR20120088644、KR20120129733、KR20130115564、TW201329200、US20030175553、US20050238919、US20060280965、US20090017330、US20090030202、US20090167162、US20090302743、US20090309488、US20100012931、US20100084966、US20100187984、US2010187984、US2012075273、US2012126221、US2013009543、US2013105787、US2013175519、US2014001446、US20140183503、US20140225088、US2014034914、US7154114、WO2001039234、WO2004093207、WO2005014551、WO2005089025、WO2006072002、WO2006114966、WO2007063754、WO2008056746、WO2009003898、WO2009021126、WO2009063833、WO2009066778、WO2009066779、WO2009086028、WO2010056066、WO2010107244、WO2011081423、WO2011081431、WO2011086863、WO2012128298、WO2012133644、WO2012133649、WO2013024872、WO2013035275、WO2013081315、WO2013191404、WO2014142472,US20170263869、US20160163995、US9466803,

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 ：CN103694277、CN1696137、EB01238981、EP01239526、EP01961743、EP1239526、EP1244155、EP1642951、EP1647554、EP1841834、EP1841834B、EP2062907、EP2730583、JP2012074444、JP2013110263、JP4478555、KR1020090133652、KR20120032054、KR20130043460、TW201332980、US06699599、US06916554、US20010019782、US20020034656、US20030068526、US20030072964、US20030138657、US20050123788、US20050244673、US2005123791、US2005260449、US20060008670、US20060065890、US20060127696、US20060134459、US20060134462、US20060202194、US20060251923、US20070034863、US20070087321、US20070103060、US20070111026、US20070190359、US20070231600、US2007034863、US2007104979、US2007104980、US2007138437、US2007224450、US2007278936、US20080020237、US20080233410、US20080261076、US20080297033、US200805851、US2008161567、US2008210930、US20090039776、US20090108737、US20090115322、US20090179555、US2009085476、US2009104472、US20100090591、US20100148663、US20100244004、US20100295032、US2010102716、US2010105902、US2010244004、US2010270916、US20110057559、US20110108822、US20110204333、US2011215710、US2011227049、US2011285275、US2012292601、US20130146848、US2013033172、US2013165653、US2013181190、US2013334521、US20140246656、US2014103305、US6303238、US6413656、US6653654、US6670645、US6687266、US6835469、US6921915、US7279704、US7332232、US7378162、US7534505、US7675228、US7728137、US7740957、US7759489、US7951947、US8067099、US8592586、US8871361、WO06081973、WO06121811、WO07018067、WO07108362、WO07115970、WO07115981、WO08035571、WO2002015645、WO2003040257、WO2005019373、WO2006056418、WO2008054584、WO2008078800、WO2008096609、WO2008101842、WO2009000673、WO2009050281、WO2009100991、WO2010028151、WO2010054731、WO2010086089、WO2010118029、WO2011044988、WO2011051404、WO2011107491、WO2012020327、WO2012163471、WO2013094620、WO2013107487、WO2013174471、WO2014007565、WO2014008982、WO2014023377、WO2014024131、WO2014031977、WO2014038456、WO2014112450.

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 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 ¹⁰¹ is selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof, when aryl or heteroaryl, have similar definitions as for Ar described above. Ar ¹ to Ar ³ have similar definitions to Ar mentioned above. k is an integer of 1 to 20. X ¹⁰¹ to X ¹⁰⁸ are 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 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 OLEDs 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,

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. 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.

E. Experimental data

Synthesis of ligand L _A2 - (9) (3) (1) (1) (1)

1-Phenyl-1H-imidazole (5.0 g,34.7mmol,1.0 eq.) was dissolved in THF (200 mL) and cooled to-78deg.C for 45 min. Butyllithium (13.9 ml,34.7mmol,1.0 eq.) was added dropwise to the stirred mixture over 30 minutes and stirred at room temperature for 2 hours. T-butylchlorodimethylsilane (5.25 g,34.7mmol,1.0 eq.) was dissolved in THF (50 mL) and added dropwise over 15 minutes. The reaction mixture was stirred at 23℃for 2 hours. The reaction was concentrated under reduced vacuum and diluted with EtOAc (500 mL), washed with saturated NaCl _(aq) (3×300 mL), water (3×300 mL), and dried over Na ₂SO₄. The mixture was concentrated under reduced pressure and purified on silica gel to give the product as a clear oil (8.0 g,31.0mmol,90% yield).

2- (Tert-Butyldimethylsilyl) -1-phenyl-1H-imidazole (4.04 g,15.48mmol,1.0 eq.) was dissolved in DCM (160 mL). N-bromobutanediamide (2.62 g,17.7mmol,0.95 eq.) is added to the stirred mixture over 15 minutes and the mixture is stirred at room temperature for 26 hours. The reaction mixture was loaded onto celite and purified on silica gel to give the pure product as a yellowish oil (4.20 g,80% yield).

5-Bromo-2- (tert-butyldimethylsilyl) -1-phenyl-1H-imidazole (4.29 g,12.7mmol,1.0 eq.) was dissolved in THF (40 mL) and the solution was cooled to-78deg.C for 45 min. Isopropyl magnesium chloride (10.8 ml,14.0mmol,1.1 eq.) was added dropwise to the stirred mixture over 15 minutes and stirred at room temperature for 2 hours. The reaction was cooled to 0deg.C and pivaloyl chloride (3.15 mL,25.4mmol,2.0 eq.) was added dropwise over 15 minutes. The reaction mixture was stirred at room temperature for 3 hours and then quenched with MeOH, diluted with EtOAc (200 mL), washed with saturated NaCl _(aq) (3×150 mL), DI water (3×150 mL), and dried over Na ₂SO₄. The mixture was concentrated under reduced pressure and purified on silica gel to give the product as a yellow glassy solid (2.2 g,12.7mmol,51% yield).

1- (2- (Tert-Butyldimethylsilyl) -1-phenyl-1H-imidazol-5-yl) -2, 2-dimethylpropan-1-one (2.00 g,5.87mmol,1 eq.) was dissolved in THF (20 mL) and the mixture was cooled to-78℃for 30 min. Methyllithium (4.40 mL,7.04mmol,1.2 eq.) was added dropwise to the solution. The reaction was stirred at-78 ℃ for 3 hours and then quenched with saturated NH ₄ Cl at 0 ℃ and diluted with EtOAc (200 mL), washed with saturated NH ₄ Cl (3×100 mL), saturated brine (3×100 mL) and water (3×100 mL). Purification on silica gel gave the product as a white solid (1.75 g,83% yield).

2- (2- (Tert-Butyldimethylsilyl) -1-phenyl-1H-imidazol-5-yl) -3, 3-dimethylbut-2-ol (1.72 g,4.87mmol,1 eq.) was dissolved in DCM (100 mL) and cooled to 0deg.C. Aluminum trichloride (3.20 g,23.9mmol 5 eq.) was added in one portion. The reaction mixture turned dark red in color and was stirred at 0 ℃ for 1 hour, followed by warming to 40 ℃ for 18 hours. The reaction mixture was cooled to 0deg.C and quenched with NaOH (aq), diluted with EtOAc (300 mL), washed with brine (3X 100 mL) and water (3X 100 mL), and dried over Na ₂SO₄. After evaporation, the crude material was dissolved in THF (50 mL) and 6N HCl (50 mL) was added at room temperature. The mixture was stirred at room temperature for 6 hours, followed by complete removal of the TBS protecting group. Purification on silica gel (120 g) gave the product as a white film (805 mg,75% yield).

4, 5-Tetramethyl-4, 5-dihydroimidazo [1,5-a ] quinoline (3.7 g,16.4mmol,1 eq.) and acetonitrile (50 mL) are added to a dry sealed tube. Methyl iodide-d 3 (1.3 mL,19.6mmol,1.2 eq.) was added to the stirred mixture. The tube was sealed and heated to 95 ℃ overnight. The solution was concentrated under reduced pressure to give a pale yellow solid. The solid was washed with ice-cold diethyl ether (100 mL) and dried in a vacuum oven to give the pure product (5.3 g,14.3mmol,88% yield) as a pale yellow solid.

Synthesis of ligand L _A 1- (3) (3) (1) (1) (1) (1) (1)

A mixture of 2- (2-aminophenyl) propan-2-ol (2.28 g,15.1 mmol), 1-iodo-2-nitrobenzene (3.75 g,15.1 mmol), S-Phos (0.495 g,1.21 mmol), pd2 (dba) 3 (0.276 g,0.302 mmol) and cesium carbonate (7.37 g,22.6 mmol) in 120mL toluene was refluxed for 20 hours. After filtration through celite and removal of the solvent, the crude material was purified by column chromatography to give 3.9g of the product as an orange solid (95%).

2- (2- ((2-Nitrophenyl) amino) phenyl) propan-2-ol (2 g,7.34 mmol) was stirred at 50℃in 50mL polyphosphoric acid and 2mL acetic acid for 12 hours. The reaction was poured into ice water and the red solid was filtered, washed with water and dried to give 1.8g of product in 96% yield.

9, 9-Dimethyl-4-nitro-9, 10-dihydroacridine (16 g,62.9 mmol) was hydrogenated in two 8g batches by stirring a solution of the starting material in EtOAc at 10% Pd/C under 50psi hydrogen. Filtration through celite and removal of solvent gave 12.2g of product (86%).

A mixture of 9, 9-dimethyl-9, 10-dihydroacridin-4-amine (12 g,53.5 mmol), triethoxymethane (7.93 g,53.5 mmol) and p-toluenesulfonic acid monohydrate (1.02 g,5.25 mmol) was stirred at 80℃for 16 hours. After combining with another 1g batch, the mixture was diluted with ethyl acetate and washed with aqueous Na2HCO 3. After drying and removal of the solvent under reduced pressure, the crude mixture was purified by column chromatography to give 11.14g of the product as a brown oil.

A mixture of 6, 6-dimethyl-6H-imidazo [4,5,1-de ] acridine (2.76 g,11.8 mmol) and iodomethane (10 g,71 mmol) in 100mL MeCN is stirred for 3 days. The resulting solid was filtered and washed with ether to give 3.5g of the product as a white solid (79%).

Synthesis of ligand L _A 1- (4) (3) (1) (1) (1) (1) (1)

2-Bromoaniline (40 g,233 mmol) was added in portions to a suspension of sodium hydride (18.60 g, 460 mmol) in THF (400 mL) at room temperature. After 2 hours, 1-bromo-2-fluoro-3-nitrobenzene (51.2 g,233 mmol) was added to THF (200 mL) at 0deg.C. The mixture was stirred at room temperature for 2 hours. The mixture was poured into ice water and extracted with DCM. The organic layer was washed with 2N HCl, dried, and the solvent was removed in vacuo. The resulting dark red oil was wet triturated with heptane to give a yellow solid, 68g (79%).

A mixture of 2-bromo-N- (2-bromophenyl) -6-nitroaniline (70 g,188 mmol), iron (105 g,1882 mmol) and NH ₄ Cl (101 g,1882 mmol) in ⁱ PrOH (500 ml)/formic acid (505 ml,1.32E+04 mmol) was heated at 80℃for 12 hours. After cooling to room temperature, the mixture was diluted with ⁱ PrOH, filtered, and the solvent was removed under reduced pressure. The residue was neutralized with aqueous NaOH and extracted with DCM. The organic phase was evaporated to give 60g of product (91%).

Butyllithium (47.7 ml,119 mmol) was added to a solution of 7-bromo-1- (2-bromophenyl) -1H-benzo [ d ] imidazole (20 g,56.8 mmol) at-10 ℃. The mixture was stirred at-10 ℃ to 0 ℃ for 1 hour, then cooled to-78 ℃. Dichlorodimethylsilane (8.07 g,62.5 mmol) was added dropwise and the solution was allowed to slowly warm to room temperature. The reaction was quenched with water, diluted with EtOAc, and the solvent was removed under reduced pressure. The crude mixture was purified by column chromatography to give the product as an orange oil, 10.9g (77%).

6, 6-Dimethyl-6H-2, 10 b-diaza-6-silaxanthene (1.31 g,5.23 mmol) and iodomethane (1.95 mL,31.4 mmol) were stirred in 40mL MeCN at room temperature for 16 hours. An additional 1mL of methyl iodide was added and the mixture was stirred for an additional 5 hours. The solvent was removed in vacuo and the residue was triturated with ether to give the product as a white solid, 1.70g (83%).

Synthesis of ligand L _A - (109) (3) (1) (1) (1)

A solution of 2-TBS-phenylimidazole in anhydrous THF (80 mL) was cooled to-78deg.C and n-BuLi (6 mL,2.5M in hexane) was added dropwise. The mixture was stirred at low temperature for 30 minutes. A solution of bromodimethyl (prop-1-en-2-yl) silane (3.98 g) (US 20190051845A 1 2019-02-14) in THF (10 mL) was added dropwise at the same temperature and allowed to stir for an additional 30 minutes. The reaction was allowed to warm slowly to room temperature and stirred for an additional 1 hour. The reaction was quenched with cold water (10 mL) and brine (20 mL) and extracted into ethyl acetate. The organics were concentrated and purified by column chromatography to give the product as a white solid (2.5 g, 47%) which was protected by refluxing a toluene solution containing 0.1 equivalent of TsOH (H ₂ O).

5- (Diisopropyll (prop-1-en-2-yl) silyl) -1-phenyl-1H-imidazole (1 g,4.13 mmol) and Eaton's reagent (14 mL) were stirred at room temperature for 16 hours. The reaction mixture was slowly poured onto cold sodium bicarbonate solution (150 mL) and extracted into EtOAc. The organic layer was concentrated and purified by column chromatography to give 760mg of product (76%).

A solution of 4, 5-tetramethyl-4, 5-dihydrobenzo [ e ] imidazo [1,5-a ] [1,3] azasilane (520 mg,2.14 mmol) and iodomethane (0.46 g,3.22 mmol) in acetonitrile (6 mL) is heated in a sealed tube at 80℃for 16 hours. The solvent was removed in vacuo and the residue was triturated in ether (60 mL) to give the product as a white solid (788 mg,96% yield).

Synthesis of ligand L _A - (111) (3) (1) (1) (1)

A solution of 2-TBS-phenylimidazole in anhydrous THF (100 mL) was cooled to-78deg.C and n-BuLi (6.2 mL,2.5M in hexane) was added dropwise. The mixture was stirred at low temperature for 30 minutes. A solution of bromodiisopropyll (prop-1-en-2-yl) silane (5.23 g,1.5 eq) (US 20190051845A 1 2019-02-14) in THF (25 mL) was added dropwise at the same temperature and allowed to stir for an additional 30 minutes. The reaction was allowed to warm slowly to room temperature and stirred for an additional 1 hour. The reaction was quenched with methanol (10 mL) and concentrated under reduced pressure at room temperature. Purification by column chromatography afforded the product as a white solid (5.15 g,84% yield) quantitatively deprotected by refluxing a toluene solution containing 0.1 equivalent of TsOH (H ₂ O).

5- (Diisopropyll (prop-1-en-2-yl) silyl) -1-phenyl-1H-imidazole (2.5 g,8.38 mmol) and Eton's reagent (28 mL) were stirred at room temperature for 16 hours. The reaction mixture was slowly poured onto cold sodium bicarbonate solution (250 mL) and extracted into EtOAc. The organic layer was concentrated and purified by column chromatography to give 1.9g of product (76%).

A solution of 4, 4-diisopropyl-5, 5-dimethyl-4, 5-dihydrobenzo [ e ] imidazo [1,5-a ] [1,3] azasilane (1.8 g,6.03 mmol) and iodomethane (1.3 g,9.05 mmol) in acetonitrile (15 mL) is heated in a sealed tube at 80℃for 16 hours. The solvent was removed in vacuo and the residue was wet triturated in ether (60 mL) to give the product as a white solid (2.35 g,88% yield).

General procedure for the preparation of the Compounds of the invention

Method A:

(a) : 2-iodo-4, 5-tetramethyl-2- (methyl-d 3) -1,2,4, 5-tetrahydroimidazo [1,5-a ] quinolin-2-ium-1-salt (1.335 g,3.59 mmol) and silver oxide (0.416 g,1.797 mmol) are suspended in dichloromethane (60 ml) containing 4A molecular sieve (1.5 g). The mixture was stirred at room temperature for 1.5 hours, at which time [ Ir (COD) Cl ] ₂ (1.2 g,1.797 mmol) was added. After stirring for one hour, the suspension was filtered through celite and the filter pad was washed with DCM (3×25 mL). The solvent was removed from the filtrate under reduced pressure to give Ir (COD) Cl (NHC) adduct (2.0 g, 96%) as a yellow solid. (b): ir (COD) Cl (NHC) complex (3.46 mmol) and 4, 4-dimethyl-3,3,7-tris (methyl-d 3) -2-phenyl-3, 4-dihydrodibenzo [ b, ij ] imidazo [2,1,5-de ] quinolizine (2.77 g,6.93 mmol) were stirred together in a 100mL round bottom flask in triethyl phosphate (20 mL) and the mixture was bubbled with nitrogen for 15 min. The mixture was heated to 150 ℃ for 16 hours. Once cooled to room temperature, the mixture was purified by column chromatography to give two hybrid face complexes as pale yellow solids.

Method B:

(a) : a mixture of 4- (methyl-d 3) -2, 5-diphenylpyridine (5.0 g,20.13 mmol) and IrCl ₃(H₂O)₃ (2.367 g,6.71 mmol) in 120mL of 3:1-ethoxyethanol in water in a 250mL round bottom flask was stirred at reflux for 16 hours. After cooling to room temperature, the yellow suspension was filtered and the solid was washed with MeOH and water to give [ L ₂IrCl]₂, 4.06g as a yellow solid. [ L ₂IrCl]₂ (4.0 g,2.77 mmol) was stirred in DCM (40 mL). Silver triflate (1.49 g, 5.81 mmol) was dissolved in methanol (20 mL) and added to the DCM solution, and the heterogeneous mixture was stirred at room temperature for 16 hours. Filtration through celite and removal of solvent from the filtrate gave 4.5g of [ L ₂Ir(MeOH)₂ ] OTf. (b): to a suspension of nitrogen-sparged [ L ₂Ir(MeOH)₂ ] OTf (2.4 g,3.7 mmol) in 1, 2-dichlorobenzene (25 mL) was added 4, 5-tetramethyl-2- (methyl-d 3) -4, 5-dihydroimidazo [1,5-a ] quinolin-2-ium-3-salt (0.9 g,3.7 mmol) and sparged with nitrogen for 5 minutes. Potassium tert-butoxide (0.6 g,7.4 mmol) was added and the reaction was heated at 80℃for 36 hours. The reaction mixture was cooled to room temperature and directly coated onto celite. Column chromatography was performed to give the desired compound, which was dissolved in THF and photoisomerized by irradiation at 350 nm. Progress was monitored by HPLC and after 1 week the reaction mixture was purified by column chromatography to give the desired facial compound as a yellow solid.

Photoluminescent properties of the compounds of the invention:

TABLE 1 Properties of examples of Compounds of the invention

The structures of the compounds of the invention listed in table 1 are as follows:

Device experiment:

The OLED was grown on a glass substrate pre-coated with an Indium Tin Oxide (ITO) layer having a sheet resistance of 15- Ω/sq. The substrate was degreased with a solvent before any organic layers were deposited or coated, and then treated with an oxygen plasma at 50W for 1.5 minutes and with UV ozone for 5 minutes at 100 mtorr. Devices were fabricated in high vacuum (< 10-6 torr) by thermal evaporation. The anode electrode is Indium Tin Oxide (ITO). Immediately after manufacture, all devices were encapsulated with epoxy-sealed glass caps in a nitrogen glove box (< 1ppm H ₂ O and O ₂), and the moisture absorbent was incorporated into the package interior.

Example OLEDs were fabricated to compare the device performance of the inventive emitter compound Ir [ L _A2-(9)(4)(1)(1)(1)]₂[L_B391 ] with the device performance of comparative compound 1. The device in table 2 has an organic layer consisting of, in order from the ITO surface: Thick compound 1 (HIL), A compound 2 (HTL) layer,Compound 3 (EBL),Compound 4 (EML) doped with 15% emitter,Compound 5 (BL),Compound 6 (ETL),Compound 7 (EIL), followed byAl (cathode). The doping percentage is in volume percent. LE is the luminous efficiency in cd/A and PE is the power efficiency in lm/W.

Table 2:

As can be seen from the device results presented herein, it was unexpectedly found that the efficiency of the compounds containing element Z of the present invention was much higher compared to the compounds not containing element Z of the present invention. Each efficiency parameter had over 10% improvement, which was considered a significant improvement.

Claims

1. A compound of formula Ir (L _A)_x(L_B)_y(L_C)_z, wherein L _A has

Wherein:

X ¹ to X ⁹ are each independently C;

R ^A、R^B and R ^C each independently represent zero substitution, mono substitution or up to the maximum allowed substitution of their associated rings;

Y is an atomic linker and Z is a diatomic linker;

Wherein Y is selected from the group consisting of:

wherein Z is selected from the group consisting of:

T ¹ and T ² are C;

R ²、R^A、R^B and R ^C are each independently hydrogen or a substituent selected from the group consisting of: deuterium, methyl, ethyl, and combinations thereof;

R and R ¹ are each independently hydrogen or a substituent selected from the group consisting of: deuterium, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, and combinations thereof;

x is 1 or 2;

y and z are each independently 0, 1 or 2; and

x+y+z＝3；

Wherein L _B and L _C are each independently selected from:

wherein:

y ¹,Y⁴ to Y ⁶ and Y ⁷ to Y ⁹ are each independently selected from C;

R _a、R_b、R_c、R_d、R_g、R_h and R _i each independently represent zero substitution, mono substitution or up to the maximum allowed substitution of their associated rings; and

R _c、R_d、R_g、R_h and R _i are each independently hydrogen or a substituent selected from the group consisting of: deuterium, methyl, ethyl, and combinations thereof;

each R _b is independently hydrogen or a substituent selected from the group consisting of: deuterium, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, and combinations thereof;

Each R _a is independently a substituent selected from the group consisting of: phenyl, biphenyl, triphenylene, fluorene, and naphthalene; and is also provided with

Either of L _A、L_B and L _C can be joined together to form a tetradentate or hexadentate ligand.

2. The compound of claim 1, wherein R, R ¹、R²、R^A、R^B and R ^C are each independently hydrogen or a substituent selected from the group consisting of: deuterium, methyl, ethyl, and combinations thereof.

3. The compound of claim 1, wherein ligand L _A has a structure according to formula I-1And is selected from the group of based on numbering scheme L _A 1- (y) (a) (i) (j) (k) (L) (m): ,

Or L _A has a structure according to formula II-1And is selected from the group based on numbering scheme L _A 2- (z) (a) (i) (j) (k);

wherein:

y is an integer from 1 to 22, z is an integer from 1 to 25, 36-52 and 172-173, a is an integer from 3 to 8, i, j, k, l and m are each independently an integer from 1 to 8; and

R ^A1 to R ^A8 have the structure defined below:

H D Me CD₃

R ^A1、R^A2、R^A3、R^A4、R^A5、R^A6、R^A7 and R ^A8.

4. The compound according to claim 3, wherein the compound is selected from the group consisting of ：Ir[(L_A1-(y)(a)(i)(j)(k)(l)(m)]₂(L_Bq)、Ir[(L_A1-(y)(a)(i)(j)(k)(l)(m)](L_Bq)₂、Ir[(L_A2-(z)(a)(i)(j)(k)]₂(L_Bq) and Ir [ (L _A2-(z)(a)(i)(j)(k)](L_Bq)₂; wherein q is an integer from 389 to 391 and 395 to 397), and

Wherein L _B389 to L _B391 and L _B395 to L _B397 have the following structures:

5. a compound, wherein the compound is selected from the group consisting of:

6. an organic light emitting device OLED comprising: an anode;

a cathode; and

An organic layer disposed between the anode and the cathode, wherein the organic layer comprises the compound of any one of claims 1-5.

7. The OLED of claim 6, wherein the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

8. The OLED of claim 7, wherein the host is selected from the group consisting of:

and combinations thereof.

9. The OLED of claim 6, wherein the compound is a sensitizer and the OLED further comprises an acceptor; and wherein the receptor is selected from the group consisting of: fluorescent emitters, delayed fluorescent emitters, and combinations thereof.

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

An anode;

a cathode; and

11. A formulation comprising a compound according to any one of claims 1-5.