WO2018113782A1 - Metal-organic complex, polymer, mixture, composition and organic electronic device - Google Patents

Abstract

Disclosed is a metal-organic complex of the general formula M(L)n(L1)m(1), wherein M(L)n is selected from one of the general formulas (2) and (3), and M is a metal atom; L is a monoanionic monodenate chelate ligand; L1 is another ligand; the formulas (A) and (B) are each independently selected from one of a double bond, an aryl group of 2 to 20 carbon atoms, a heteroaryl group of 2 to 20 carbon atoms, and a non-aromatic ring group of 2 to 20 carbon atoms, and at most one of the formulas (A) and (B) in the general formula (3) is a double bond; Ar3 is selected from one of aromatic ring systems of 2 to 20 carbon atoms, heteroaromatic ring systems of 2 to 20 carbon atoms, and non-aromatic ring systems of 2 to 20 carbon atoms; -X- is a single bond, or, X is a secondary bridging group; n is any integer from 1 to 3; m is any integer from 0 to 4; and o is any integer from 0 to 2.

Description

Metal organic complexes, polymers, mixtures, compositions and organic electronic devices Technical field:

The present invention relates to the field of organic electronic devices, and more particularly to a metal organic complex, a high polymer, a mixture, a composition, and an organic electronic device.

Background technique:

In flat panel display and lighting applications, organic light-emitting diodes (OLEDs) have the advantages of low cost, light weight, low operating voltage, high brightness, color adjustability, wide viewing angle, easy assembly to flexible substrates, and low energy consumption. Therefore, it has become the most promising display technology. In order to improve the luminous efficiency of organic light emitting diodes, various systems based on fluorescent and phosphorescent materials have been developed. An organic light-emitting diode using a fluorescent material has high reliability, but its internal electroluminescence quantum efficiency is limited to 25% under electric field excitation. In contrast, since the branch ratio of the singlet excited state and the triplet excited state of the excitons is 1:3, an organic light emitting diode using a phosphorescent material can achieve an internal luminescence quantum efficiency of almost 100%. For small molecule OLEDs, the triplet excitation is effectively obtained by doping the center of the heavy metal, which improves the spin-orbital merging and thus the inter-system transition to the triplet state.

Metal ruthenium (III)-based complexes are a class of materials widely used in high-efficiency OLEDs with high efficiency and stability. Baldo et al. reported the use of fac-tris(2-phenylpyridine)ruthenium(III)[Ir(ppy) ₃ ] as a phosphorescent material, 4,4'-N,N'-dicarbazole-biphenyl (4 , 4'-N, N'-diarbazole-biphenyl) (CBP) is a high quantum efficiency OLED of matrix material (Appl. Phys. Lett. 1999, 75, 4). Another example of a phosphorescent luminescent material is the sky blue complex bis[2-(4',6'-difluorophenyl)pyridine-N,C ² ]-pyridinium ruthenium (III) (FIrpic), which is doped to The high triplet energy matrix exhibits an extremely high photoluminescence quantum efficiency of approximately 60% in solution and almost 100% in solid film (Appl. Phys. Lett. 2001, 79, 2082). Although ruthenium (III) systems based on 2-phenylpyridine and its derivatives have been used in large quantities for the preparation of OLEDs, phosphorescent luminescent materials containing other metal centers with these ligands have not been fully investigated.

Despite increasing interest in phosphorescent materials, particularly metal complexes with heavy metal centers, most efforts have focused on the use of cerium (III), platinum (II), copper (I) and cerium (II). Other metal centers are rarely noticed. Unlike isoelectronic platinum (II) complexes, which are known to exhibit high-efficiency luminescent properties, examples of luminescent gold (III) complexes are rarely reported, which may be derived from the low energy dd of gold (III) metal centers. The presence of the coordination field (LF) and the electrophilicity of the gold (III) metal center. One way to improve the luminous efficiency of gold (III) complexes is to introduce strong σ-donor ligands, such as the stable gold (III) aryl compounds first discovered and synthesized by Yam et al., even at room temperature. Interesting photoluminescence properties (J. Chem. Soc., Dalton Trans. 1993, 1001). Another interesting donor is an alkynyl group. Although the luminescent properties of the gold (I) alkynyl complex have been extensively studied, the chemistry of the gold (III) alkynyl group has been largely ignored, with one exception: the 6-benzyl-2,2'-bipyridine alkyne The synthesis of the compound of the fund (III) (J. Chem. Soc. Dalton Trans. 1999, 2823), but its luminescent properties have not been studied. Yam et al. disclose the synthesis of a series of bis-cyclometalated acetylene fund (III) compounds using various strong σ-donor alkynyl ligands, all of which exhibit in various media at room and low temperatures. Very strong luminescent properties (J. Am. Chem. Soc. 2007, 129, 4350). In addition, the external quantum efficiency of OLEDs prepared using these luminescent gold (III) compounds as phosphorescent dopant materials was 5.5%. These luminescent gold (III) compounds contain a tridentate ligand and at least one strong σ-donor group coordinated to the gold (III) metal center. Since then, Yam et al. have reported a new class of phosphorescent materials for metallized acetylene fund (III) complexes (J. Am. Chem. Soc. 2010, 132, 14273). The optimized vapor-deposited OLED achieves a current efficiency of 11.5% EQE and 37.4 cd A ^-1 . This indicates that the acetylene fund (III) complex is a promising luminescent material. However, the stability of such compounds is low.

Summary of the invention:

Based on this, a metal organic complex with high stability is provided.

In addition, a high polymer, a mixture, a composition, and an organic electronic device are also provided.

A metal organic complex having the general formula M(L) _n (L ₁ ) _m (1), wherein M(L) _{n is} selected from one of the following formulae:

M is a metal atom;

L is a monoanionic monodentate chelating ligand;

L ₁ is a bidentate chelate ligand or a tridentate chelate ligand;

Each independently selected from the group consisting of a double bond, an aryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a non-aromatic ring group having 2 to 20 carbon atoms, and being substituted by R An aryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms substituted by R, and a non-aromatic ring group having 2 to 20 carbon atoms substituted by R One, and in the formula (3),

At most one of them is a double bond;

Ar _{3 is} selected from the group consisting of an aryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a non-aromatic ring group having 2 to 20 carbon atoms, and having 2 substituted by R One of an aryl group of 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms substituted by R, and a non-aromatic ring group of 2 to 20 carbon atoms substituted by R;

R is selected from the group consisting of hydrogen, hydrazine, a halogen atom, a linear alkane group having 1 to 20 carbon atoms, a branched alkane group having 1 to 20 carbon atoms, and a linear olefin having 1 to 20 carbon atoms. a branched olefin group having 1 to 20 carbon atoms, an alkane ether group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a heteroaryl group and one of non-aromatic ring groups having 1 to 20 carbon atoms, wherein one or more R groups may be bonded to each other to form an aliphatic ring system or an aromatic ring system, or Formula 2 or 3 bonding to form an aliphatic ring system or an aromatic ring system;

-X- is a single bond, or X is a two bridging group;

n is any integer from 1 to 3;

m is any integer from 0 to 4;

o is any integer from 0 to 2.

A high polymer comprising a repeating unit, the structural formula of the repeating unit comprising the structural formula of the above metal organic complex.

A mixture comprising the above metal organic complex and one of the above polymers and an organic functional material.

A composition comprising the above metal organic complex, the above-mentioned high polymer, and one of the above mixtures, and an organic solvent.

An organic electronic device comprising a functional layer, and the material of the functional layer comprises one of the above metal organic complex, the above-mentioned high polymer, the above mixture, and the above composition.

Details of one or more embodiments of the invention are set forth in the accompanying drawings and description below. Other features, objects, and advantages of the invention will be apparent from the description and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS:

1 is a photoluminescence spectrum of metal organic complexes prepared in Examples 1, 3, 4 and 5.

detailed description

In order to facilitate the understanding of the present invention, the present invention will be described more fully hereinafter with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that the understanding of the present disclosure will be more fully understood.

All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined. The terminology used in the description of the present invention is for the purpose of describing particular embodiments, and is not intended to limit the invention.

The metal organic complex of one embodiment has the following general formula:

M(L) _n (L ₁ ) _m (Formula 1);

Wherein M is a metal atom; L is a monoanionic monodentate chelate ligand; L ₁ is a bidentate chelate ligand or a tridentate chelate ligand; n is any integer from 1 to 3; m is 0 to 4 Any integer.

Further, the substructure M(L) _{n of the} metal organic complex is selected from one of the following formulas:

among them,

M is a metal atom;

Each independently selected from the group consisting of a double bond, an aryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a non-aromatic ring group having 2 to 20 carbon atoms, and being substituted by R An aryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms substituted by R, and a non-aromatic ring group having 2 to 20 carbon atoms substituted by R One, and in the formula (3),

At most one of them is a double bond;

Ar _{3 is} selected from the group consisting of an aryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a non-aromatic ring group having 2 to 20 carbon atoms, and having 2 substituted by R One of an aryl group of 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms substituted by R, and a non-aromatic ring group of 2 to 20 carbon atoms substituted by R;

R is selected from the group consisting of hydrogen, hydrazine, a halogen atom, a linear alkane group having 1 to 20 carbon atoms, a branched alkane group having 1 to 20 carbon atoms, and a linear olefin having 1 to 20 carbon atoms. a branched olefin group having 1 to 20 carbon atoms, an alkane ether group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a heteroaryl group and one of non-aromatic ring groups having 1 to 20 carbon atoms, wherein one or more R groups may be bonded to each other to form an aliphatic ring system or an aromatic ring system, or Formula 2 or 3 bonding to form an aliphatic ring system or an aromatic ring system;

-X- is a single bond, or X is a two bridging group;

n is any integer from 1 to 3;

m is any integer from 0 to 4;

o is any integer from 0 to 2.

Further, M is a transition metal atom. Still further, M is selected from the group consisting of ruthenium, gold, platinum, rhodium, ruthenium, osmium, iridium, nickel, copper, silver, zinc, tungsten, and palladium. Further, M is selected from one of gold, platinum, and palladium. Specifically, M is gold. Gold is chemically stable and has a significant heavy atomic effect, enabling metal organic complexes to achieve high luminous efficiency.

In one of the embodiments, o is one. At this time, M is directly connected to N. In another embodiment, o is zero.

further,

And Ar ₃ are each independently selected from one of an aromatic ring group having 5 to 20 ring atoms and a heteroaromatic ring group having 5 to 20 ring atoms. further,

And Ar _{3 is} each selected from the group consisting of an aromatic cyclic group having 5 to 18 ring atoms and a heteroaromatic ring group having 5 to 18 ring atoms. go a step further,

And Ar ₃ are each independently selected from one of an aromatic ring group having 5 to 12 ring atoms and a heteroaromatic ring group having 5 to 18 ring atoms.

Among them, the aromatic group (aryl group) means a hydrocarbon group containing at least one aromatic ring, and includes a monocyclic group and a polycyclic ring system. The heteroaromatic group (heteroaryl) refers to a hydrocarbon group (containing a hetero atom) containing at least one heteroaromatic ring, and the hydrocarbon group of the heteroaromatic ring includes a monocyclic group and a polycyclic ring system. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. These ring species of polycyclic ring, at least one ring species are aromatic or heteroaromatic. Among them, an aromatic group or a heteroaryl group in an aromatic ring group or a heteroaromatic ring group may be interrupted by a short non-aromatic unit. Among them, the non-aromatic unit is less than 10% of a non-hydrogen atom. Further, the non-aromatic unit is less than 5% of a non-hydrogen atom. For example, the non-aromatic unit is a carbon atom, a nitrogen atom or an oxygen atom. Therefore, ring systems such as 9,9'-spirobifluorene, 9,9-diarylsulfonium, triarylamine and diaryl ether are also considered to be Aromatic ring system.

Specifically, the aromatic group is selected from the group consisting of benzene, a derivative of benzene, a derivative of naphthalene, naphthalene, a derivative of ruthenium, osmium, a derivative of phenanthrene, phenanthrene, a perylene, a derivative of perylene, Derivatives of tetracene and tetracene, derivatives of ruthenium and osmium, derivatives of benzopyrene, benzopyrene, derivatives of triphenylene, triphenylene, derivatives of ruthenium and osmium, derivatives of ruthenium and osmium One of them.

Specifically, the heteroaromatic group is selected from the group consisting of furan, a derivative of furan, a derivative of benzofuran, benzofuran, a derivative of thiophene, thiophene, a derivative of benzothiophene, benzothiophene, pyrrole, pyrrole Derivatives, derivatives of pyrazoles, pyrazoles, derivatives of triazoles, triazoles, imidazoles, derivatives of imidazoles, derivatives of oxazoles, oxazoles, oxadiazoles, derivatives of oxadiazoles, thiazoles, Derivatives of thiazole, derivatives of tetrazole, tetrazole, derivatives of ruthenium and osmium, derivatives of oxazole, oxazole, pyrroloimidazole, derivatives of pyrroloimidazole, pyrrolopyrrole, pyrrolopyrrole Derivatives, thienopyrroles, derivatives of thienopyrrole, derivatives of thienothiophene, thienothiophene, derivatives of furopyrrol, furopyrroles, furanfurans, derivatives of furanfuran, thieno Derivatives of furan, thienofuran, benzisoxazole, derivatives of benzisoxazole, benzisothiazole, derivatives of benzisothiazole, benzimidazole, derivatives of benzimidazole, pyridine, Derivatives of pyridine, pyrazine, pyridyl Derivatives, derivatives of pyridazines, pyridazines, derivatives of pyrimidines, pyrimidines, derivatives of triazines, triazines, derivatives of quinolines, quinolines, derivatives of isoquinolines, isoquinolines, neighbors Derivatives of diazonaphthalene, o-naphthyridine, quinoxalines, derivatives of quinoxalines, derivatives of phenanthridine, phenanthridine, derivatives of pyridine, pyridine, quinazoline, quinazoline One of a derivative of a quinazolinone and a quinazolinone.

In one of the embodiments,

And Ar ₃ are each independently selected from the group consisting of an unsubstituted non-aromatic ring group having 5 to 20 ring atoms and a non-aromatic ring group having 5 to 20 ring atoms substituted by R ₀ to improve The triplet level of the metal organic complex to obtain a green or blue light emitter.

Among them, the ring of the non-aromatic ring group contains at least two carbon atoms. Further, the ring of the non-aromatic ring group contains 2 to 6 carbon atoms. The ring of the non-aromatic ring group may be a saturated ring and a partially saturated ring. The non-aromatic ring group includes an unsubstituted non-aromatic ring group and a non-aromatic ring group substituted with R.

R ₀ contains a hetero atom. Further, R ₀ includes at least one of Si, N, P, O, S, and Ge. Further, R ₀ contains at least one of Si, N, P, O, and S. For example, R ₀ may be a group of a cyclohexyl- or piperidine-like system, or a group of a cyclooctadiene-like ring system.

Specifically, R _{0 is} selected from one of a C ₁ - C ₁₀ alkyl group, a C ₁ - C ₁₀ alkoxy group, a C ₂ - C ₁₀ aryl group, and a C ₂ - C ₁₀ heteroaryl group. Wherein C ₁ -C ₁₀ alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2 -methylbutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2, 2,2-Trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, One of cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl and octynyl.

Wherein the C ₁ -C ₁₀ alkoxy group is selected from the group consisting of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and One of 2-methylbutoxy groups.

Among them, the C ₂ -C ₁₀ aryl group and the C ₂ -C ₁₀ heteroaryl group can be further substituted by the above R ₀ and can be bonded to an aromatic ring or a heteroaromatic ring.

Specifically, the C ₂ -C ₁₀ aryl group or the C ₂ -C ₁₀ heteroaryl group is selected from the group consisting of benzene, naphthalene, anthracene, anthracene, anthracene, fluorene, fluorene, fluorene, butyl, pentane, benzo.芘, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, thiopurine, pyrrole, hydrazine, isoindole, carbazole, pyridine, quinoline, iso Quinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, Carbazole, imidazole, benzimidazole, naphthimidazole, phenamimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinimidazole, oxazole, benzoxazole, naphthoxazole, indoloxazole, Phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzoxazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, diazepine, 1,5-naphthyridine, carbazole, benzoporphyrin, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3 -oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4 -thiadiazole, 1,2,5-thiadiazole, 1,3,4- Thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole. One of 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, anthracene, pteridine, guanidinium and benzothiadiazole Kind.

It is to be noted that the aromatic ring group and the heteroaromatic ring group are not limited to the above groups, and may also be selected from the group consisting of a biphenylylene group, a linoleylene, an anthracene, a spirobifluorene, a dihydrophenanthrene, a tetrahydroanthracene and an anthracene. One of 芴 (cis or trans).

further,

And Ar ₃ are each selected from one of the following formulas:

among them,

A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ are each independently selected from one of CR ₃ and N;

Y ^{1 is} selected from one of CR ₄ R ₅ , SiR ₄ R ₅ , NR ₃ , C(=O), S and O;

R ₃ , R ₄ and R ₅ are each selected from the group consisting of H, D, a linear alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a thioalkoxy group, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, having a thioalkoxy group of 3 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a substituted ketone group having 1 to 20 carbon atoms, and having 2 to 20 carbon atoms Alkoxycarbonyl, aryloxycarbonyl having 7 to 20 carbon atoms, cyano (-CN), carbamoyl (-C(=O)NH ₂ ), haloformyl (-C(=O) -X, wherein X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF ₃ , Cl, Br, F, crosslinkable groups, aryl groups having 5 to 40 ring atoms, heteroaryl groups having 5 to 40 ring atoms, and aryloxy groups having 5 to 40 ring atoms At least one of a group and a heteroaryloxy group having 5 to 40 ring atoms. Among them, R ³ , R ⁴ and R ⁵ can bond to an aliphatic ring group or an aromatic ring group, and R ³ , R ⁴ and R ⁵ themselves can also bond to an aliphatic ring group or an aromatic ring group, respectively. The crosslinkable group means a functional group containing an unsaturated bond such as an alkenyl group or an alkynyl group.

go a step further,

Each of them is independently selected from the group consisting of a cyclic aromatic hydrocarbon group, an aromatic heterocyclic group, and a group having 2 to 10 ring structures. Wherein the cycloaromatic hydrocarbon group is selected from the group consisting of phenyl, biphenyl, triphenyl, benzo, naphthyl, anthryl, phenalkenyl, phenanthryl, anthracenyl, fluorenyl, fluorenyl, fluorenyl and fluorenyl One of the aromatic heterocyclic groups selected from the group consisting of dibenzothiophenyl, dibenzofuranyl, furyl, thienyl, benzofuranyl, benzothienyl, oxazolyl, pyrazolyl, imidazolyl, Triazolyl, isoxazolyl, thiazolyl, oxadiazolyl, oxatriazole, oxazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl ,oxazinyl, oxathiazinyl, oxadiazinyl, fluorenyl, benzimidazolyl, oxazolyl, pyridazinyl, benzoxazolyl, benzoisoxazolyl, benzothiazolyl, Quinolinyl, isoquinolyl, o-diaza(hetero)naphthyl, quinazolinyl, quinoxalinyl, naphthyl, anthracenyl, pteridinyl, xanthylene, acridinyl, phenazinyl , phenothiazine, phenoxazinyl, dibenzoselenophene, benzoselenophene, benzofuran pyridyl, oxazolyl, pyridinium, pyrrole dipyridyl, furan dipyridyl Benzothiophenyridyl, thiophene One of a pyridyl group, a benzoselenopyridyl group and a selenophenodipyridinyl group; a group having 2 to 10 ring structures selected from the group consisting of a cyclic aromatic hydrocarbon group and an aromatic heterocyclic group, and a ring structure is attached. Together, or the ring structure is bonded together by 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.

Among them, each

It can be further substituted with at least one of an anthracene, an alkyl group, an alkoxy group, an amino group, an alkene group, an alkyne group, an aralkyl group, a heteroalkyl group, an aryl group, and a heteroaryl group.

specifically,

And Ar ₃ are each selected from one of the following groups:

among them,

And H on the ring of Ar ₃ can be arbitrarily substituted.

In one embodiment, X is a non-aromatic bridging group. Further, X is selected from a linear alkane group having 0 to 10 carbon atoms, a branched alkane group having 0 to 10 carbon atoms, a linear olefin group having 0 to 10 carbon atoms, and having 0 Branched olefin group of -10 carbon atoms, alkane ether group of 0 to 10 carbon atoms, O, S, S=O, SO ₂ , N(R), B(R), Si(R) ₂ , Ge(R) ₂ , P(R), P(=O)R, P(R) ₃ , Sn(R) ₂ , C(R) ₂ , C=O, C=S, C=Se, C=N(R) ₂ , C=C(R) ₂ , one of an aromatic ring group containing 5 to 20 carbon atoms and a heteroaromatic ring group containing 4 to 20 carbon atoms. Wherein R is independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkane group having 1 to 20 carbon atoms, a branched alkane group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. Alkane ether group, alkane aromatic ring group having 1 to 20 carbon atoms, alkane heteroaromatic ring group having 1 to 20 carbon atoms, and alkane non-aromatic ring group having 1 to 20 carbon atoms One of them.

Further, X is selected from a linear alkane group having 0 to 5 carbon atoms, a branched alkane group having 0 to 5 carbon atoms, a linear olefin group having 0 to 5 carbon atoms, and a branched olefin group of 0 to 5 carbon atoms, having 0 to 5 One of an alkane ether group of a carbon atom, an aromatic ring group of 5 to 15 carbon atoms, and a heteroaromatic ring group of 4 to 15 carbon atoms.

Further, X is selected from a linear alkane group having 0 to 2 carbon atoms, a branched alkane group having 0 to 2 carbon atoms, a linear olefin group having 0 to 2 carbon atoms, and having a branched olefin group of 0 to 2 carbon atoms, an alkane ether group having 0 to 2 carbon atoms, an aromatic ring group having 5 to 10 carbon atoms, and a heteroaromatic group containing 4 to 10 carbon atoms One of the group of ring groups.

Specifically, X is selected from one of the following structural formulas:

Wherein R ₆ , R ₇ , R ₈ and R ₉ are each independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkane group having 1 to 20 carbon atoms, and a branched alkane having 1 to 20 carbon atoms. a linear olefin group having 1 to 20 carbon atoms, a branched olefin group having 1 to 20 carbon atoms, an alkane ether group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms An aryl group of an atom, a heteroaryl group having 1 to 20 carbon atoms, and a non-aromatic ring group having 1 to 20 carbon atoms, wherein R ₆ , R ₇ , R ₈ and R ₉ The aliphatic ring system or the aromatic ring system may be bonded to each other or to each other, or may be bonded to the formula 2 or 3, respectively, to form an aliphatic ring system or an aromatic ring system.

More specifically, X is selected from one of the following structures:

In one of the embodiments, M(L) _n comprises one of the following substructures:

Wherein # represents a position connected to Ar ₃ or M in the general formula (3); -Z ¹ -, -Z ² - and -Z ³ - are each independently selected from a single bond, -N(R)-, -C (R) ₂ -, -Si(R) ₂ -, -O-, -S-, -C=N(R)-, -C=C(R) ₂ - and -P(R)- Species

Each independently selected from the group consisting of an aryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a non-aromatic ring group having 2 to 20 carbon atoms, and having 2 substituted by R One of an aryl group of 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms substituted by R, and a non-aromatic cyclic group having 2 to 20 carbon atoms substituted by R.

Further, M(L) _n includes one of the following substructures:

Wherein, # indicates a position connected to Ar ₃ or M in the general formula (3); -Z ¹ -, -Z ² - and -Z ³ - are each independently selected from a single bond, -N(R)-, - Among C(R) ₂ -, -Si(R) ₂ -, -O-, -S-, -C=N(R)-, -C=C(R) ₂ - and -P(R)- One.

Specifically, M(L) _n includes one of the following substructures:

Wherein # represents a position connected to Ar ₃ or M in the formula (3); the above substructure formula can be further substituted.

In one embodiment, o is 1, Ar ₃ and M are connected by a σ-bond, and Ar ₃ is a strong sigma-donor ligand of a negative ion monodentate.

In one embodiment, Ar _{3 is} selected from the group consisting of benzene, naphthalene, anthracene, anthracene, phenanthrene, anthracene, oxazole, imidazole, and benzimidazole.

Further, the metal organic complex is selected from one of the following formulae:

among them,

X ⁷¹ to X ⁷³ are each selected from the group consisting of a nitrogen atom, an oxygen atom, and a carbon atom. Further, at least one of X ⁷¹ to X ⁷³ is a nitrogen atom;

R ¹⁶ to R ²¹ are each selected from the group consisting of hydrogen, hydrazine, a halogen atom, CN, NO ₂ , CF ₃ , B(OR ² ) ₂ , Si(R ² ) ₃ , and a linear alkane group having 1 to 20 carbon atoms. a branched alkane group having 1 to 20 carbon atoms, a linear olefin group having 1 to 20 carbon atoms, a branched olefin group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms An alkane ether group of an atom, an alkane sulfide group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, a heteroaryl group having 1 to 20 carbon atoms, and having 1 to 20 One of the non-aromatic ring groups of one carbon atom;

L is a monoanionic monodentate chelating ligand, which has the same definition as L in the above M(L) _n . .

In one embodiment, the above metal-organic complex facilitates obtaining thermally excited delayed fluorescent TADF or so-called Singlet Harvesting characteristics. According to the principle of thermally excited delayed fluorescent TADF material disclosed in Adachi et al., Nature Vol 492, 234, (2012), when the ΔE(S1-T1) of the metal organic compound is sufficiently small, the triplet excitons of the organic compound can pass the opposite Converts internally to singlet excitons for efficient illumination.

Specifically, ΔE(S1-T1) of the metal organic complex is ≤0.30 eV. Further, the metal organic complex has ΔE(S1-T1)≤0.25 eV. Still further, the metal organic complex has ΔE(S1-T1) ≤ 0.20 eV. Further, ΔE(S1-T1) ≤ 0.10 eV of the metal organic complex. Where ΔE(S1-T1) is the difference between the singlet energy level S1 and the triplet energy level T1.

It should be noted that the absolute values of HOMO, LUMO, S1 and T1 depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, for example, the starting point and the peak point on the CV curve can be given differently. HOMO/LUMO value. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. In this embodiment, the values of HOMO, LUMO, S1, and T1 are based on Time-dependent DFT simulations, but do not affect the application of other measurement or calculation methods.

Specifically, the metal organic complex is selected from one of the following structures:

In one embodiment, the metal organic complex is a luminescent material, and the metal organic complex has an emission wavelength of 300 nm to 1000 nm. Further, the metal organic complex has an emission wavelength of 350 nm to 900 nm. Further, the metal organic complex has an emission wavelength of 400 nm to 800 nm. Among them, luminescence refers to photoluminescence or electroluminescence. Further, the photoluminescence efficiency of the metal organic complex is ≥30%. Still further, the photoluminescence efficiency of the metal organic complex is ≥ 40%. Still further, the photoluminescence efficiency of the metal organic complex is ≥50%. Further, the photoluminescence efficiency of the metal organic complex is ≥60%.

In another embodiment, the metal organic complex is a non-luminescent material.

The high polymer of one embodiment includes a repeating unit, and the structural formula of the repeating unit includes the structural formula of the above metal organic complex. In the present embodiment, the high polymer is a non-conjugated high polymer, and for example, the structural unit of the metal organic complex represented by the general formula (1) is on the side chain of the high polymer. In another embodiment, the high polymer is a conjugated high polymer.

The use of the above metal organic complexes or polymers in organic electronic devices. The organic electronic device is selected from the group consisting of an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, and an organic spintronic device. One of an organic sensor and an organic plasmon emitting diode (Organic Plasmon Emitting Diode). Further, the organic electronic device is an OLED. Specifically, the above metal organic complex is used in the light-emitting layer of the OLED device.

A mixture of an embodiment comprising one of a metal organic complex and a high polymer, and an organic functional material.

The organic functional material is selected from the group consisting of a hole injection material (HIM), a hole transport material (HTM), an electron transport material (ETM), an electron injecting material (EIM), an electron blocking material (EBM), and a hole blocking material (HBM). One of an organic matrix material (Host), a singlet illuminant (fluorescent illuminant), a thermally activated delayed fluorescent luminescent material (TADF), a triplet illuminant (phosphorescent illuminant), and an organic dye. Further, the organic functional material is selected from one of a luminescent metal organic complex and an organic dye. In particular, the organic functional material may also be an organic functional material as disclosed in WO2010135519A1, US20090134784A1 and WO2011110277A1.

The organic functional material may be a small molecule or a high polymer material. Small molecules as used herein refer to molecules that are non-polymeric, non-oligomer, non-dendritic, and non-blend, with no repeating structures in small molecules. Among them, the molar mass of the small molecule is ≤3000 g/mol. Further, the molar mass of the small molecule is ≤ 2000 g/mol. Further, the molar mass of the small molecule is ≤1500 g/mol.

The polymer comprises a homopolymer, a copolymer, and a block copolymer. Also in this application, the high polymer also contains dendrimers. For the synthesis and application of dendrimers, see Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles Introduction to N. Moorefield, Fritz Vogtle.

A conjugated polymer is a type of high polymer. The backbone of the conjugated polymer is mainly composed of sp ² hybrid orbitals of carbon atoms. For example: polyacetylene and poly(phenylene vinylene), the carbon atoms in the main chain can also be substituted by other non-carbon atoms, and the sp ² hybridization of carbon atoms in the main chain is interrupted by some natural defects. At the time, it is still considered to be a conjugated polymer. In addition, in the present application, the conjugated polymer may also contain an aryl amine, an aryl phosphine, and other heteroarmotics, metal organic complexes in the main chain. (organometallic complexes) and so on.

In one embodiment, the mixture comprises a metal organic complex and an organic functional material, and the metal organic complex has a mass percentage of 0.01% to 30%. Further, the metal organic complex has a mass percentage of 0.1% to 20%. Further, the metal organic complex has a mass percentage of 0.2% to 15%. Further, the metal organic complex has a mass percentage of 2% to 15%.

In one embodiment, the mixture comprises one of a metal organic complex and a high polymer, and a triplet matrix material material. Wherein, the metal organic complex as the phosphorescent emitter, the weight percentage of the metal organic complex ≤ 30 wt%; further, the weight percentage of the metal organic complex ≤ 20 wt%; further, the weight percentage of the metal organic complex ≤ 15 wt% .

In another embodiment, the mixture includes one of a metal organic complex and a high polymer, a triplet matrix material, and a triplet emitter.

In another embodiment, the mixture comprises one of a metal organic complex and a high polymer, and a thermally activated delayed fluorescent luminescent material (TADF).

The following is a detailed description of the triplet matrix material, the triplet emitter and the TADF material (but is not limited thereto).

1, triplet matrix material (TripletHost):

Any metal complex or organic compound can be used as a matrix for the triplet matrix material as long as its triplet energy is higher than that of the illuminant, especially higher than that of the triplet emitter (phosphorescent emitter).

Specifically, the metal complex of the triplet matrix material has the following general formula:

Wherein M is a metal; (Y ³ -Y ⁴ ) is a bidentate ligand; Y ³ and Y ⁴ are each independently selected from one of C, N, O, P and S; L is an auxiliary ligand; As an integer, the value of m has a maximum coordination number from 1 to M; m+n is the maximum coordination number of M.

In one embodiment, M is selected from the group consisting of Cu, Au, Ir, and Pt.

Further, the metal complex of the triplet matrix material has the following general formula:

Wherein (O-N) is a bidentate ligand, and the metal is coordinated to the O atom and the N atom.

Among them, the organic compound which can be used as the triplet matrix material is a compound containing a cyclic aromatic hydrocarbon group or a compound containing an aromatic heterocyclic group. Among them, the compound containing a cyclic aromatic hydrocarbon group includes: benzene, biphenyl, triphenyl, benzo and anthracene; and the compound containing an aromatic heterocyclic group includes: dibenzothiophene, dibenzofuran, dibenzoselenophene , furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, carbazole, pyridinium, pyrrole dipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, dioxin Oxazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazide, dioxazin, hydrazine, benzimidazole, oxazole, evil Azole, dibenzoxazole, benzoxazole, benzothiazole, quinoline, isoquinoline, o-naphthyridine, quinazoline, quinoxaline, naphthalene, anthracene, pteridine, xanthene, anthracene Pyridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furopypyridine, benzothiophenepyridine, thienopyridine, benzoselenopyridine and selenophene pyridine.

Further, the organic compound which can be used as the triplet matrix material may also be a group containing a 2-ring to 10-ring structure, for example, a cyclic aromatic hydrocarbon group or an aromatic heterocyclic group. Wherein each group is directly connected, or through an oxygen atom, a nitrogen atom, At least one of a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group is bonded. Further, each aromatic group (Ar) is substituted with one of hydrogen, an alkyl group, an alkoxy group, an amino group, an alkenyl group, an alkynyl group, an aralkyl group, a heteroalkyl group, an aryl group, and a heteroaryl group.

In one embodiment, the organic compound of the triplet matrix material comprises at least one of the following groups:

Wherein n is any integer from 0 to 20; X ¹ -X ⁸ are each selected from one of CR ¹ and N; X ^{9 is} selected from one of CR ¹ R ² and NR ¹ ; R ^{1 -} R ⁷ Each is independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

Specifically, the triplet matrix material is selected from one of the following structures:

2. Triplet emitter (Triplet Emitter)

Triplet emitters are also known as phosphorescent emitters. The triplet emitter is a metal complex containing the formula M(L)n. Wherein M is a metal element, L is an organic ligand, and L is bonded to M through one or more position linkages or coordination; n is an integer greater than 1, preferably n is selected from 1, 2, 3, 4 One of 5, 6 and 6.

Further, the metal complex is coupled to the polymer through one or more locations. Specifically, the metal complex is coupled to the polymer via an organic ligand.

Further, M is selected from one of a transition metal element, a lanthanoid element, and a lanthanoid element. Preferably, M is selected from one of Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu, and Ag. More preferably, M is selected from one of Os, Ir, Ru, Rh, Cu, Au, and Pt.

Among them, the triplet emitter contains a chelating ligand, that is, a ligand. The ligand is coordinated to the metal by at least two bonding sites. Further, the triplet emitter comprises 2 to 3 bidentate ligands or polydentate ligands. Chelating ligands are beneficial for increasing the stability of metal complexes.

The organic ligand is selected from the group consisting of a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, and a 2-phenylquinoline derivative. One of them. Further, the organic ligands may all be substituted, for example by fluorine or trifluoromethyl. The ancillary ligand is selected from one of acetic acid acetone and picric acid.

Specifically, the metal complex of the triplet emitter has the following general formula:

Where M is a metal. Preferably, M is selected from one of a transition metal element, a lanthanoid element, and a lanthanide element;

Ar ¹ is a cyclic group, wherein Ar ¹ contains at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, and the cyclic group is coordinated to the metal through a donor atom;

Ar ² is a cyclic group, wherein Ar ² contains at least one C atom, and the cyclic group is bonded to the metal through a C atom;

Ar ¹ and Ar ² are bonded together by a covalent bond; Ar ¹ and Ar ² each may carry one or more substituent groups, and Ar ¹ and Ar ² may be further coupled together by a substituent group;

L is an ancillary ligand. Preferably, L is a bidentate chelate ligand. More preferably, L is a monoanionic bidentate chelate ligand;

m is any integer from 1 to 3. Preferably, m is 2 or 3. More preferably, m is 3;

n is any integer from 0 to 2. Preferably, n is 0 or 1. More preferably, n is zero.

The material of the triplet illuminant and its use can be WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010102709, US 20070087219 A1, US 20090061681 A1, US 20010053462 A1, Baldo, Thompson et al. Nature 403, (2000), 750-753, US 20090061681 A1, US 20090061681 A1, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624, J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124, Kido et al. .Lett. 657, 1990, US 2007/0252517 A1, Johnson et al., JACS 105, 1983, 1795, Wrighton, JACS 96, 1974, 998, Ma et al., Synth. Metals 94, 1998, 245, US 6824895 US 7029766, US 6835469, US 6830828, US 20010053462 A1, WO 2007095118 A1, US 2012004407A1, WO 2012007088A1, WO2012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 10228215 The material of the triplet emitter disclosed in 0A and WO 2009118087A1 and its use.

Specifically, the triplet emitter is selected from one of the following structures:

3. Thermally activated delayed fluorescent luminescent material (TADF):

Conventional organic fluorescent materials can only use electro-excitation to form 25% of singlet exciton luminescence, and organic electronic devices have lower internal quantum efficiency (up to 25%). Although the phosphorescent material enhances the inter-system traversal due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the organic electronic device reaches 100%. However, the problems of expensive phosphorescent materials, poor material stability, and severe roll-off of device efficiency limit their application in OLEDs. The thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔEst), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. Therefore, the singlet excitons and triplet excitons formed under electrical excitation can be fully utilized, so that the quantum efficiency in the organic electronic device can reach 100%.

TADF needs to have a small singlet-triplet energy level difference (ΔEst). Among them, ΔEst of the TADF is <0.3 eV. Further, ΔEst of the TADF is <0.2 eV. Further, ΔEst of the TADF is <0.1 eV. Further, ΔEst of the TADF is <0.05 eV.

In one embodiment, the TADF may be CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064(A1), Adachi, et. al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett., 101 , 2012, 093306, Adachi, et.al. Chem. Commun., 48, 2012, 11392, Adachi, et. al. Nature Photonics, 6, 2012, 253, Adachi, et. al. Nature, 492, 2012, 234 , Adachi, et.al.J.Am.Chem.Soc, 134, 2012, 14706, Adachi, et.al.Angew.Chem.Int.Ed, 51, 2012, 11311, Adachi, et.al.Chem.Commun .,48,2012,9580,Adachi,et.al.Chem.Commun.,48,2013,10385,Adachi,et.al.Adv.Mater.,25,2013,3319,Adachi,et.al.Adv. Mater., 25, 2013, 3707, Adachi, et. al. Chem. Mater., 25, 2013, 3038, Adachi, et. al. Chem. Mater., 25, 2013, 3766, Adachi, et.al. TADF as disclosed in Mater. Chem. C., 1, 2013, 4599 and Adachi, et. al. J. Phys. Chem. A., 117, 2013, 5607.

Specifically, the TADF is selected from one of the following structures:

In one of the embodiments, the metal organic complex is used in an evaporated OLED device. Wherein, the molar mass of the metal organic complex is ≤1000 g/mol; further, the molar mass of the metal organic complex is ≤900 g/mol; further, the molar mass of the metal organic complex is ≤850 g/mol; further, the metal The molar mass of the organic complex is ≤800 g/mol; further, the molar mass of the metal organic complex is ≤700 g/mol.

In another embodiment, a metal organic complex is used to print an OLED device. Wherein, the molar mass of the metal organic complex is ≥700 g/mol; further, the molar mass of the metal organic complex is ≥800 g/mol; further, the molar mass of the metal organic complex is ≥900 g/mol; further, the metal The molar mass of the organic complex is ≥1000 g/mol; further, the molar mass of the metal organic complex is ≥1100 g/mol.

Wherein, when the metal organic complex is used for printing the OLED device, the solubility of the metal organic complex in toluene is ≥5 mg/mL at 25 ° C; further, the solubility of the metal organic complex in toluene is ≥ 8 mg / mL; The solubility of the metal organic complex in toluene is ≥10 mg/mL.

The composition of one embodiment includes one of the above metal organic complex, the above polymer, and the above mixture, and an organic solvent.

In one embodiment, when the composition is used as a printing ink, the composition may be a solution or a suspension. Viscosity and surface tension are important parameters of the composition. The surface tension parameters of suitable compositions are suitable for the particular substrate and the particular printing process.

Wherein, when the composition is used as a printing ink, the surface tension of the composition is at an operating temperature or at 25 ° C. 19dyne/cm to 50dyne/cm. Further, the composition has a surface tension of 22 dyne/cm to 35 dyne/cm. Further, the surface tension of the composition is from 25 dyne/cm to 33 dyne/cm.

In another embodiment, when the composition is used in ink jet printing, the viscosity of the composition is from 1 cps to 100 cps at an operating temperature or 25 °C. Further, the viscosity of the composition is from 1 cps to 50 cps. Still further, the viscosity of the composition is from 1.5 cps to 20 cps. Further, the viscosity of the composition is from 4.0 cps to 20 cps.

Viscosity can be adjusted by a number of methods, for example, by selecting a solvent and adjusting the concentration of the functional material in the composition. Among them, the above composition can appropriately adjust the viscosity of the composition according to the printing method. When the above composition includes a metal organic complex, an organic functional material, and an organic solvent, or includes a high polymer, an organic functional material, and an organic solvent, the organic functional material has a mass percentage of 0.3% to 30%. Further, the organic functional material has a mass percentage of 0.5% to 20%. Further, the organic functional material has a mass percentage of 0.5% to 15%. Further, the organic functional material has a mass percentage of 0.5% to 10%. Further, the organic functional material has a mass percentage of 1% to 5%.

Wherein, the organic solvent includes a first solvent, and the first solvent includes at least one of an aromatic solvent, a heteroaromatic solvent, a ketone solvent, an ether solvent, and an ester solvent. Further, the aromatic solvent is selected from one of an aliphatic chain-substituted aromatic solvent and a ring-substituted aromatic solvent.

Specifically, the aromatic solvent is selected from the group consisting of p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, and p-methyl Propylene, dipentylbenzene, trimerene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4- Tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 1,3 -dipropoxybenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, N-methyldiphenylamine, 4-iso Propylbiphenyl, 1,1-dichlorodiphenylmethane, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene and dibenzyl ether One kind.

Specifically, the heteroaromatic solvent is selected from one of 2-phenylpyridine, 3-phenylpyridine, and 4-(3-phenylpropyl)pyridine.

Specifically, the ketone solvent is selected from the group consisting of 1-tetralone, 2-tetralone, 2-(phenyl epoxy)tetralone, 6-(methoxy)tetralone, acetophenone, Phenylacetone, benzophenone, 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methyl Propiophenone, isophorone, 2,6,8-trimethyl-4-indanone, anthrone, 2-nonanone, 3-fluorenone, 5-nonanone, 2-nonanone, 2,5- One of adipone, phorone and di-n-pentyl ketone.

Specifically, the ether solvent is selected from the group consisting of 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1 ,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-B Basic diethyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidyl phenyl ether, Dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether , 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, pentyl ether c hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethyl One of diol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

The ester solvent is selected from the group consisting of alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkanolactone and oil. One of the acid alkyl esters.

Further, the first solvent includes at least one of an aliphatic ketone and an aliphatic ether. Among them, the aliphatic ketone is selected from 2-壬 Ketone, 3-fluorenone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, 2,6,8-trimethyl-4-indanone, phorone and di-n-pentanone At least one; the aliphatic ether is selected from the group consisting of pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, three At least one of ethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

In another embodiment, the organic solvent further includes a second solvent, and the second solvent includes methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, and benzene. Ether, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxy Toluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl At least one of sulfone, tetrahydronaphthalene, decalin and hydrazine.

When the above composition is used as a coating or printing ink, it can be applied to the preparation of an organic electronic device. Further, the above composition is prepared by a method of printing or coating an organic electronic device.

Wherein, the printing or coating method is selected from, but not limited to, inkjet printing, Nozzle Printing, letterpress printing, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roller printing, One of lithography, flexographic printing, rotary printing, spray coating, brush coating, pad printing, nozzle printing (Nozzle printing), and slit type extrusion coating. Further, the printing or coating method is selected from one of inkjet printing, slit type extrusion coating, jet printing, and gravure printing.

In one embodiment, the above composition further comprises an additive selected from at least one of a surface active compound, a lubricant, a wetting agent, a dispersing agent, a hydrophobic agent, and a binder. The additive is used to adjust the viscosity, film forming properties, adhesion, and the like of the composition.

For more information on printing techniques and solutions, such as solvents and concentrations, viscosity, etc., see Handbook of Print Media: Technologies and Production Methods, edited by Helmut Kipphan. ISBN 3-540-67326-1.

An organic electronic device according to an embodiment includes a functional layer, and the material of the functional layer includes one of the above-described metal organic complex and the above-mentioned high polymer. Further, the organic electronic device comprises a cathode, an anode and a functional layer between the cathode and the anode, and the material of the functional layer comprises one of the above metal organic complex and the above high polymer.

The organic electronic device is selected from the group consisting of an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, and an organic spintronic device. One of an organic sensor and an organic plasmon emitting diode (Organic Plasmon Emitting Diode). Further, the organic electronic device is an electroluminescent device. Further, the organic electronic device is an OLED, wherein the OLED comprises a substrate, an anode, a light emitting layer and a cathode.

Among them, the substrate may be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting component. The substrate may be a substrate as disclosed in Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. Further, the substrate is selected from the group consisting of plastics, metals, semiconductor wafers, and glass. Specifically, the substrate has a smooth surface. More specifically, the surface of the substrate is free from defects.

In one embodiment, the substrate is flexible and the substrate is a polymeric film or plastic. Among them, the glass transition temperature Tg of the substrate is 150 ° C or higher. Further, the glass transition temperature Tg of the substrate is 200 ° C or higher. Further, the glass transition temperature Tg of the substrate is 250 ° C or higher. Further, the substrate has a glass transition temperature Tg of 300 ° C or more. Specifically, the flexible substrate is polyethylene terephthalate (PET) or polyethylene glycol (2,6-naphthalene) (PEN).

Wherein the anode comprises one of a conductive metal, a metal oxide and a conductive polymer. The anode can easily inject holes into a hole injection layer (HIL), a hole transport layer (HTL), or a light-emitting layer. In one embodiment, the work function of the anode and the absolute difference in energy level between the HOMO levels of the illuminants in the luminescent layer, or the work function of the anode and the p-type semiconductor material as HIL or HTL or electron blocking layer (EBL) The absolute value of the difference between the HOMO level or the valence band level is less than 0.5 eV. Further, the work function of the anode and the absolute value of the energy level difference between the HOMO levels of the illuminants in the luminescent layer, or the work function of the anode and the HOMO level of the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) Or the absolute value of the difference in the valence band energy level is less than less than 0.3 eV. Further, the work function of the anode and the absolute value of the energy level difference between the HOMO levels of the illuminants in the luminescent layer, or the work function of the anode and the HOMO energy of the p-type semiconductor material as HIL or HTL or electron blocking layer (EBL) The absolute value of the difference of the level or valence band level is less than less than 0.2 eV.

The anode material includes, but not limited to, Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. The anode material can be obtained by a method of technical deposition, such as physical vapor deposition, including RF magnetron sputtering, vacuum thermal evaporation, and electron beam (e-beam).

In one of the embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to make organic electronic devices.

Wherein the cathode comprises one of a conductive metal and a metal oxide, and the cathode can easily inject electrons into the EIL or ETL or directly into the light-emitting layer. In one of the embodiments, the work function of the cathode and the absolute value of the LUMO energy level difference of the illuminant in the luminescent layer, or the work function of the cathode and the electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer The absolute value of the difference between the LUMO level or the conduction band level of the (HBL) n-type semiconductor material is less than 0.5 eV. Further, the work function of the cathode and the absolute value of the LUMO energy level difference of the illuminant in the luminescent layer, or the work function of the cathode and n as an electron injection layer (EIL) or an electron transport layer (ETL) or a hole blocking layer (HBL) The absolute value of the difference between the LUMO level or the conduction band level of the type semiconductor material is less than 0.3 eV. Further, the work function of the cathode and the absolute value of the LUMO energy level difference of the illuminant in the luminescent layer, or the work function of the cathode and the electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) The absolute value of the difference between the LUMO level or the conduction band level of the n-type semiconductor material is less than 0.2 eV.

In general, materials useful as cathodes for OLEDs can be used as cathode materials for organic electronic devices. The cathode material is one selected from the group consisting of Al, Au, Ag, Ca, Ba, Mg, LiF/Al, Mg/Ag alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, and ITO. The cathode material can be prepared by physical vapor deposition. Among them, the physical vapor deposition method includes radio frequency magnetron sputtering, vacuum thermal evaporation, and electron beam (e-beam).

Further, the OLED further includes other functional layers selected from the group consisting of a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), and an electron transport layer (ETL). And one of a hole blocking layer (HBL).

In one embodiment, the organic electronic device includes a light-emitting layer comprising one of the above-described metal organic complexes and high polymers. Wherein, the luminescent layer is prepared by vacuum evaporation or solution processing.

Wherein, when the organic electronic device is a light emitting device, the organic electronic device has an emission wavelength of 300 nm to 1000 nm. Further, the organic electronic device has an emission wavelength of 350 nm to 900 nm. Further, the organic electronic device has an emission wavelength of 400 nm to 800 nm.

The above organic electronic device can be applied to an electronic device. The electronic device includes a display device, a lighting device, a light source, a sensor, and the like.

Part of the specific embodiment:

Example 1

The synthetic steps of the metal organic complex Au-1 of the present embodiment are as follows:

(1) Synthesis of precursor A

Precursor A was synthesized by the method disclosed in J. Am. Chem. Soc. 2007, 129, 4350 in a yield of 45%.

(2) Synthesis of metal organic complex Au-1

Sodium hydride (60 wt% in mineral oil, 17 mg, 0.43 mmol) was weighed into a 100 mL three-necked flask in a nitrogen-filled atmosphere, washed with hexane, and the above clarified portion was removed by decantation. Dehydrated THF (20 mL) was added thereto, followed by carbazole (72 mg, 0.43 mmol) and stirred at room temperature. The reaction was started as a suspension, and after about 1 hour, the precursor A (198 mg, 0.43 mmol) was added to give an orange solution. After further stirring at room temperature for one day, the solvent was distilled off under reduced pressure, and the obtained solid was dissolved in chlorobenzene (100 mL) and passed through a short column of alumina. The fraction was concentrated under reduced pressure, and recrystallized from hexanes to give a red powdery compound of Compound 1-1.

Example 2

The synthetic steps of the metal organic complex Au-2 of this embodiment are as follows:

(1) Synthesis of precursor A

Precursor A was synthesized by the method disclosed in J. Am. Chem. Soc. 2007, 129, 4350 in a yield of 45%.

(2) Synthesis of metal organic complex Au-2

Sodium hydride (60 wt% in mineral oil, 17 mg, 0.43 mmol) was weighed into a 100 mL three-necked flask in a nitrogen-filled atmosphere, washed with hexane, and the above clarified portion was removed by decantation. Dehydrated THF (20 mL) was added thereto, followed by diphenylamine (73 mg, 0.43 mmol) and stirred at room temperature. The reaction was started as a suspension, and after about 1 hour, the precursor A (198 mg, 0.43 mmol) was added to become a red solution. After further stirring at 60 ° C for one day, the solvent was distilled off under reduced pressure, and the obtained solid was dissolved in chlorobenzene (100 mL) and passed through a short column of alumina. Distilling the fraction under reduced pressure Recrystallization was carried out by adding an appropriate amount of hexane to obtain a red powder of the compound Au-2 in a yield of 35%.

Example 3

The synthetic steps of the metal organic complex Au-3 of the present embodiment are as follows:

(1) Synthesis of precursor A

Precursor A was synthesized by the method disclosed in J. Am. Chem. Soc. 2007, 129, 4350 in a yield of 45%.

(2) Synthesis of metal organic complex Au-3

4-bromotriphenylamine (139 g, 0.43 mmol), magnesium flakes (1032 mg, 43 mmol) were placed in a dry two-necked flask, vacuum-filled with nitrogen three times, then 15 mL of dehydrated THF was added, and a small amount of iodine was added to initiate the Grignard. The reaction was refluxed at 60 ° C for 4 hours to prepare a Grignard reagent, which was used as it was. Precursor A (198 mg, 0.43 mmol) and 15 mL of dehydrated THF were placed in a separate reaction flask, and the Grignard reagent prepared above was added dropwise with a syringe. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, and then heated to 60 ° C for one day, and the reaction liquid became green. Then, the solvent was evaporated under reduced pressure, and the obtained solid was dissolved in chlorobenzene (100 mL) and passed through a short column of alumina. . The fraction was concentrated under reduced pressure, and recrystallized from hexanes to give a yellow powdery compound of Au-3.

Example 4

The synthetic steps of the metal organic complex Au-4 of this embodiment are as follows:

(1) Synthesis of precursor A

Precursor A was synthesized by the method disclosed in J. Am. Chem. Soc. 2007, 129, 4350 in a yield of 45%.

(2) Synthesis of metal organic complex Au-4

Sodium hydride (60 wt% in mineral oil, 17 mg, 0.43 mmol) was weighed into a 100 mL three-necked flask in a nitrogen-filled atmosphere, washed with hexane, and the above clarified portion was removed by decantation. Dehydrated THF (20 mL) was added thereto, followed by addition of 3,6-di-tert-butylcarbazole (120 mg, 0.43 mmol). The reaction was started as a suspension, and after about 1 hour, the precursor A (198 mg, 0.43 mmol) was added to give an orange solution. After further stirring at room temperature for one day, the solvent was distilled off under reduced pressure, and the obtained solid was dissolved in chlorobenzene (100 mL) and passed through a short column of alumina. The fraction was concentrated under reduced pressure, and then recrystallized from hexanes to give a red powdery compound of Au-4.

Example 5

The synthetic steps of the metal organic complex Au-5 of the present embodiment are as follows:

(1) Synthesis of precursor A

Precursor A was synthesized by the method disclosed in J. Am. Chem. Soc. 2007, 129, 4350 in a yield of 45%.

(2) Synthesis of intermediate B

First, p-methylphenylsulfonyl chloride (7.6 g, 40 mmol) and 3,7-dibromocarbazole (9.75 g, 30 mmol) in potassium hydroxide (2.24 g, 40 mmol) in 100 mL of acetone and reacted at room temperature 3 hour. The solvent was then evaporated under reduced pressure, and the obtained solid was dissolved in methylene chloride (100 mL). The resulting white solid (9.54 g, 20 mmol) and carbazole (8.35 g, 50 mmol), potassium phosphate (20.2 g, 100 mmol), cuprous iodide (1 g, 5 mmol), 1,4-diaminocyclohexane (1 mL, 5 mmol), in 150 mL of 1,4-dioxane (20 mL), refluxed at 130 ° C under nitrogen for 24 h, cooled to room temperature, water was added to the reaction solution, extracted with dichloromethane, and the organic phase was washed with water. dried over anhydrous magnesium sulfate, and concentrated, then purified by column, and then to give a white solid (1.956g, 3mmol), was added sodium hydroxide (2g, 50mmol), in a ratio of 50: 20: 20THF: MeOH: H 2 The mixture was stirred at 80 ° C for 24 hours under O to give a white solid (yield: 35%).

(3) Synthesis of metal organic complex Au-5

Sodium hydride (60 wt% in mineral oil, 17 mg, 0.43 mmol) was weighed into a 100 mL three-necked flask in a nitrogen-filled atmosphere, washed with hexane, and the above clarified portion was removed by decantation. Dehydrated THF (20 mL) was added thereto, followed by Intermediate B (214 mg, 0.43 mmol). The reaction was started as a suspension, and after about 1 hour, the precursor A (198 mg, 0.43 mmol) was added to give an orange solution. After further stirring at room temperature for one day, the solvent was distilled off under reduced pressure, and the obtained solid was dissolved in chlorobenzene (100 mL) and passed through a short column of alumina. The fraction was concentrated under reduced pressure, and then recrystallized from hexanes to give a yellow powdery compound of Au-5.

Example 6

The synthetic steps of the metal organic complex Au-6 of this embodiment are as follows:

(1) Synthesis of precursor A

Precursor A was synthesized by the method disclosed in J. Am. Chem. Soc. 2007, 129, 4350 in a yield of 45%.

(2) Synthesis of metal organic complex Au-6

Sodium hydride (60 wt% in mineral oil, 17 mg, 0.43 mmol) was weighed into a 100 mL three-necked flask in a nitrogen-filled atmosphere, washed with hexane, and the above clarified portion was removed by decantation. Dehydrated THF (20 mL) was added thereto, followed by the addition of benzopyrene (51 mg, 0.43 mmol). The reaction was started as a suspension, and after about 1 hour, the precursor A (198 mg, 0.43 mmol) was added to give an orange solution. After further stirring at room temperature for one day, the solvent was distilled off under reduced pressure, and the obtained solid was dissolved in chlorobenzene (100 mL) and passed through a short column of alumina. The fraction was concentrated under reduced pressure. Recrystallization was carried out by adding an appropriate amount of hexane to obtain a yellow powder of compound Au-6 in a yield of 43%.

test:

1. Determination of the energy structure of metal organic complexes

The energy levels of the metal organic complexes Au-1, Au-2, Au-3, Au-4, Au-5, and Au-6 obtained in Examples 1 to 6 can be obtained by quantum calculation, for example, using TD-DFT (including Time-Frequency Functional Theory) By Gaussian03W (Gaussian Inc.), the specific simulation method can be found in WO2011141110. First, use the semi-empirical method "Ground State/Hartree-Fock/Default Spin/LanL2MB" (Charge 0/Spin Singlet) to optimize the molecular geometry. Then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method. Calculated as "TD-SCF/DFT/Default Spin/B3PW91/gen geom=connectivity pseudo=lanl2" (Charge 0/Spin Singlet). The HOMO and LUMO levels are calculated according to the following calibration formula, and S1 and T1 are used directly.

HOMO(eV)=((HOMO(Gaussian)×27.212)-0.9899)/1.1206

LUMO(eV)=((LUMO(Gaussian)×27.212)-2.0041)/1.385

Among them, HOMO(G) and LUMO(G) are direct calculation results of Gaussian 03W, and the unit is Hartree. The results are shown in Table 1:

Table 1 Energy structure of the metal organic complexes obtained in Examples 1 to 6

material	HOMO[eV]	LUMO[eV]	T1[eV]	S1[eV]
Au-1	-5.18	-3.18	1.87	1.89
Au-2	-5.06	-3.00	1.88	2.01
Au-3	-5.19	-2.90	2.41	2.44
Au-4	-5.11	-3.13	1.85	1.87
Au-5	-5.25	-3.39	1.79	1.80
Au-6	-5.70	-3.28	2.31	2.60

2. Detection of photophysical properties of metal organic complexes

The metal organic complexes obtained in Examples 1, 3, 4 and 5 were subjected to photoluminescence (PL) spectroscopy, and the results are shown in Fig. 1.

It can be seen from Fig. 1 that in the photoluminescence spectrum of the solids of Au-1, Au-3, Au-4 and Au-5, the maximum peaks of the emission spectra of all the carbazole gold (III) complexes are located at 500 nm. Between 700 nm, this type of complex is described as suitable for use in yellow and red light electronics.

3, OLED device detection

The OLED device was prepared by using the metal organic complexes obtained in Examples 1 to 6, respectively, and the specific steps are as follows:

a, cleaning of the conductive glass substrate: when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;

b, HTL (60 nm), EML (45 nm), ETL (35 nm): The metal organic complexes obtained in Examples 1 to 6 were thermally evaporated to a function in a high vacuum (1 × 10 ^-6 mbar, mbar), respectively. In the layer;

c, cathode: LiF / Al (1nm / 150nm) in a high vacuum (1 × 10 ^-6 mbar) in the thermal evaporation;

d. Package: The device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.

The OLED devices prepared by the metal organic complexes obtained in Examples 1 to 6 each have the following structure:

OLED device 1: ITO/NPD (60 nm) / 15% Au-1: mCP (45 nm) / TPBi (35 nm) / LiF (1 nm) / Al (150 nm) / cathode;

OLED device 2: ITO/NPD (60 nm) / 15% Au-2: mCP (45 nm) / TPBi (35 nm) / LiF (1 nm) / Al (150 nm) / cathode;

OLED device 3: ITO/NPD (60 nm) / 15% Au-3: mCP (45 nm) / TPBi (35 nm) / LiF (1 nm) / Al (150 nm) / cathode;

OLED device 4: ITO/NPD (60 nm) / 15% Au-4: mCP (45 nm) / TPBi (35 nm) / LiF (1 nm) / Al (150 nm) / cathode;

OLED device 5: ITO/NPD (60 nm) / 15% Au-5: mCP (45 nm) / TPBi (35 nm) / LiF (1 nm) / Al (150 nm) / cathode;

OLED device 6: ITO/NPD (60 nm) / 15% Au-6: mCP (45 nm) / TPBi (35 nm) / LiF (1 nm) / Al (150 nm) / cathode.

test:

The current-voltage luminance (JVL) characteristics of OLED devices 1 through 6 are characterized by characterization equipment while recording important parameters such as efficiency and external quantum efficiency.

The maximum external quantum efficiencies of the OLED devices 1 to 6 were tested to be 10.2%, 7.6%, 8.8%, 9.8%, 6.4%, and 2.4%, respectively.

Further optimization, such as device structure optimization, combined optimization of HTM, ETM and host materials, will further improve the performance of OLED devices, especially efficiency, drive voltage and lifetime.

The technical features of the above-described embodiments may be arbitrarily combined. For the sake of brevity of description, all possible combinations of the technical features in the above embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be considered as the scope of this manual.

The above-described embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims (16)

1. A metal organic complex having the general formula M(L) _n (L ₁ ) _m (1), wherein M(L) _{n is} selected from one of the following formulae:

   

   and

   

   M is a metal atom;

   L is a monoanionic monodentate chelating ligand;

   L _{1 is} selected from the group consisting of a bidentate chelating ligand and a tridentate chelating ligand;

   

   Each independently selected from the group consisting of a double bond, an aryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a non-aromatic ring group having 2 to 20 carbon atoms, and being substituted by R An aryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms substituted by R, and a non-aromatic ring group having 2 to 20 carbon atoms substituted by R One, and in the formula (3),

   

   At most one of them is a double bond;

   Ar _{3 is} selected from the group consisting of an aryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a non-aromatic ring group having 2 to 20 carbon atoms, and having 2 substituted by R One of an aryl group of 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms substituted by R, and a non-aromatic ring group of 2 to 20 carbon atoms substituted by R;

   R is selected from the group consisting of hydrogen, hydrazine, a halogen atom, a linear alkane group having 1 to 20 carbon atoms, a branched alkane group having 1 to 20 carbon atoms, and a linear olefin having 1 to 20 carbon atoms. a branched olefin group having 1 to 20 carbon atoms, an alkane ether group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a heteroaryl group and one of non-aromatic ring groups having 1 to 20 carbon atoms;

   -X- is a single bond, or X is a two bridging group;

   n is any integer from 1 to 3;

   m is any integer from 0 to 4;

   o is any integer from 0 to 2.
2. The metal organic complex according to claim 1, wherein the M is selected from the group consisting of ruthenium, gold, platinum, rhodium, ruthenium, osmium, iridium, nickel, copper, silver, zinc, tungsten and palladium. .
3. The metal-organic complex according to any one of claims 1 to 2, wherein

   

   And Ar ₃ are each independently selected from one of the following formulas:

   

   among them,

   A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are each independently selected from one of CR ₃ and N;

   Y ^{1 is} selected from one of CR ₄ R ₅ , SiR ₄ R ₅ , NR ₃ , C(=O), S and O;

   R ₃ , R ₄ and R ₅ are each independently selected from H, D, a linear alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and having 1 to 20 carbon atoms. a thioalkoxy group of an atom, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, a thioalkoxy group having 3 to 20 carbon atoms, a silyl group having 3 to 20 carbon atoms, a substituted ketone group having 1 to 20 carbon atoms, having 2 to 20 carbon atoms Alkoxycarbonyl group, aryloxycarbonyl group having 7 to 20 carbon atoms, cyano group, carbamoyl group, haloformyl group, formyl group, isocyano group, isocyanate group, thiocyanate group, isothiocyanate Acid ester group, hydroxyl group, nitro group, CF ₃ , Cl, Br, F, crosslinkable group, aryl group having 5 to 40 ring atoms, heteroaryl group having 5 to 40 ring atoms, At least one of an aryloxy group having 5 to 40 ring atoms and a heteroaryloxy group having 5 to 40 ring atoms.
4. The metal-organic complex according to any one of claims 1 to 2, wherein the X is selected from one of the following structural formulae:

   

   

   

   and

   

   Wherein R ₆ , R ₇ , R ₈ and R ₉ are each independently selected from the group consisting of hydrogen, deuterium, a halogen atom, a linear alkane group having 1 to 20 carbon atoms, and a branched alkane having 1 to 20 carbon atoms. a linear olefin group having 1 to 20 carbon atoms, a branched olefin group having 1 to 20 carbon atoms, an alkane ether group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms One of an aryl group of an atom, a heteroaryl group having 1 to 20 carbon atoms, and a non-aromatic ring group having 1 to 20 carbon atoms.
5. The metal-organic complex according to any one of claims 1 to 2, wherein the M(L) _n comprises one of the following substructures:

   

   and

   

   Wherein # represents a position connected to Ar ₃ or M in the general formula (3); -Z ¹ -, -Z ² - and -Z ³ - are each independently selected from a single bond, -N(R)-, -C (R) ₂ -, -Si(R) ₂ -, -O-, -S-, -C=N(R)-, -C=C(R) ₂ - and -P(R)- Species

   

   and

   

   Each independently selected from the group consisting of an aryl group having 2 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a non-aromatic ring group having 2 to 20 carbon atoms, and having 2 substituted by R One of an aryl group of 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms substituted by R, and a non-aromatic cyclic group having 2 to 20 carbon atoms substituted by R.
6. The metal organic complex according to claim 5, wherein the M(L) _n comprises one of the following substructures:

   

   Wherein -Z ¹ -, -Z ² - and -Z ³ - are each independently selected from the group consisting of a single bond, -N(R)-, -C(R) ₂ -, -Si(R) ₂ -, -O-, One of -S-, -C=N(R)-, -C=C(R) ₂ - and -P(R)-.
7. The metal-organic complex according to any one of claims 1 to 2, wherein the o is 1, and Ar ₃ is a strong σ-donor ligand of a negative ion monodentate.
8. The metal organic complex according to any one of claims 1 to 2, wherein the Ar _{3 is} selected from the group consisting of benzene, naphthalene, anthracene, anthracene, phenanthrene, anthracene, oxazole, imidazole and benzimidazole. Kind.
9. The metal organic complex according to any one of claims 1 to 2, wherein the metal organic complex is selected from one of the following formulae:

   

   

   and

   

   among them,

   X ⁷¹ to X ⁷³ are each selected from the group consisting of a nitrogen atom, an oxygen atom and a carbon atom;

   R ¹⁶ to R ²¹ are each selected from the group consisting of hydrogen, hydrazine, a halogen atom, CN, NO ₂ , CF ₃ , B(OR ² ) ₂ , Si(R ² ) ₃ , and a linear alkane group having 1 to 20 carbon atoms. a branched alkane group having 1 to 20 carbon atoms, a linear olefin group having 1 to 20 carbon atoms, a branched olefin group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms An alkane ether group of an atom, an alkane sulfide group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, a heteroaryl group having 1 to 20 carbon atoms, and having 1 to 20 One of the non-aromatic ring groups of one carbon atom;

   L is a monoanionic monodentate chelating ligand.
10. The metal-organic complex according to any one of claims 1 to 2, wherein the metal organic complex is selected from one of the following structures:

    

    and

    
11. A high polymer comprising a repeating unit, the structural formula of the repeating unit comprising the structural formula of the metal organic complex according to any one of claims 1 to 10.
12. A mixture comprising one of the metal organic complex according to any one of claims 1 to 10 and the high polymer according to claim 11 and an organic functional material.
13. The mixture according to claim 12, wherein the organic functional material is selected from the group consisting of a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, an electron blocking material, a hole blocking material, and an organic matrix material. One of a singlet illuminant, a thermally activated delayed fluorescent luminescent material, a triplet illuminant, and an organic dye.
14. A composition comprising one of the metal-organic complex according to any one of claims 1 to 10, the high polymer according to claim 11 and the mixture according to any one of claims 12 to 13, and Organic solvents.
15. An organic electronic device comprising a functional layer, the material of the functional layer comprising the metal organic complex according to any one of claims 1 to 10, the high polymer according to claim 11, and any one of claims 12 to 13. And a mixture of the composition of claim 14.
16. The organic electronic device according to claim 15, wherein the organic electronic device is selected from the group consisting of an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, and an organic self. One of a spin-on device, an organic sensor, and an organic plasmon emitting diode.

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