CN109790183A

CN109790183A - Metal organic complex and its application, mixture, organic electronic device

Info

Publication number: CN109790183A
Application number: CN201780059807.4A
Authority: CN
Inventors: 潘君友; 梁志明; 黄宏
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2016-12-13
Filing date: 2017-12-13
Publication date: 2019-05-21
Also published as: WO2018108110A1

Abstract

A kind of metal organic complex and its application, mixture, organic electronic device, shown in the structure of the metal organic complex such as general formula (1), the definition of the symbol in the general formula (1) is identical as in specification.

Description

Metal organic complex and its application, mixture, organic electronic device

This application claims Patent Office of the People's Republic of China is submitted on December 13rd, 2016, application No. is 201611148194.5, the priority of the Chinese patent application of entitled " a kind of metal organic complex and its in the application of electronic device ", entire contents are hereby incorporated by reference in the application.

Technical field

The present invention relates to organic photoelectrical material technical fields, more particularly to a kind of metal organic complex and its application, mixture, organic electronic device.

Background technique

In flat-panel monitor and illumination application, Organic Light Emitting Diode (Organic Light-Emitting Diode, OLED) there is low cost, light weight, low-work voltage, high brightness, color tunability, wide viewing angle, be easily assembled in flex substrate and the advantage of low-energy-consumption, thus as the display technology for most having development potentiality.It is various to be developed based on fluorescence and phosphorescent light-emitting materials system in order to improve the luminous efficiency of Organic Light Emitting Diode.Using the Organic Light Emitting Diode of fluorescent material, there is higher reliability, but its internal electroluminescence quantum efficiency is restricted to 25% under electric field excitation.In contrast, since the singlet excited of exciton and the branching ratio of triplet excited state are 1:3,100% internal illumination quantum efficiency can be almost obtained using the Organic Light Emitting Diode of phosphor material.For small molecule OLED, triplet excitation is effectively obtained by doping heavy metal center, to improve spin orbit coupling, and thus intersystem crossing to triplet.

Complex based on metal iridium (III) is widely used in a kind of material of high efficiency OLEDs, efficiency and stability with higher.Baldo et al., which is reported, uses fac- tri- (2- phenylpyridine) iridium (III) [Ir (ppy) 3] as phosphorescent light-emitting materials, 4,4 '-N,-two carbazoles of N '-biphenyl (4,4 '-N, N '-diarbazole-biphenyl) (CBP) be host material high-quantum efficiency OLED (Appl.Phys.Lett.1999,75,4).Another example of phosphorescent light-emitting materials be sky blue complex it is bis- [2- (4 ', 6 '-difluorophenyl) pyridine-N, C2]-pyrrole formic acid iridium (III) (FIrpic), it shows in about solution 60% and the almost 100% high photoluminescence quantum efficiencies (Appl.Phys.Lett.2001 in solid film when being doped in high triplet energy matrix, 79,2082).Although iridium (III) system based on 2- phenylpyridine and its derivative has been largely used to preparation OLEDs, the phosphorescent light-emitting materials containing other metal centers with these ligands are still studied without inabundant yet substantially.

It is most of to make great efforts still to concentrate on using iridium (III), platinum (II), copper (I) and shackles (II) although the interest of the especially metal complex with heavy metal center is growing day by day to phosphorescent light-emitting materials.Other metal centers are seldom concerned.Different from known equal electronics platinum (II) complex for showing efficient tuorbillion light property, the example of luminous gold (III) complex seldom reports that this may originate from the presence in the ligand field low energy d-d (LF) possessed by golden (III) metal center and the electrophilicity of golden (III) metal center.A kind of mode for the luminous efficiency improving golden (III) complex is to introduce strong σ-donor ligands, stable gold (III) aryl compound for finding and synthesizing earliest such as Yam et al., interesting photic tuorbillion light property (J.Chem.Soc. is even also shown at room temperature, Dalton Trans.1993,1001).Another interesting donor is alkynyl.Although the tuorbillion light property of golden (I) Complexes with Alkynyl of numerous studies, but the chemistry of golden (III) alkynyl is substantially ignored, in addition to an exception: 6- Benzyl base -2,2 ' synthesis (the J.Chem.Soc.Dalton Trans.1999 of golden (III) compound of the alkynyl of-bipyridyl, 2823), but its tuorbillion optical property was still without studying.Yam et al. discloses a series of synthesis of double-Cyclometalated golden (III) compounds of alkynyl using various strong σ-donor alkynyl ligands, wherein all compounds all show the very strong characteristics of luminescence (J.Am.Chem.Soc.2007 in various media under room temperature and low temperature, 129,4350).In addition, gold (III) compound for using these luminous is as OLEDs external quantum efficiency prepared by phosphorescent dopant material up to 5.5%.These luminescent gold (III) compounds contain a tridentate ligand and at least one is coordinated to strong σ-donor groups on golden (III) metal center.Hereafter, Yam et al. reports the novel phosphor material (J.Am.Chem.Soc.2010,132,14273) of one kind of golden (III) complex of metallization alkynyl in succession.Vapor deposition type OLED by optimization reaches the current efficiency of 11.5% EQE and 37.4cd A-1.This shows that golden (III) complex of alkynyl is promising luminescent material.But it is still necessary to improve for the stability of such compound.

Simultaneously and luminous efficiency is not reduced to improve the stability and device lifetime of golden (III) complex, and a kind of scheme is one Tridentate ligand and monodentate ligand combine, and the tetradentate ligands of more coordinate bonds are formed, to obtain more stable complex.Tetradentate ligands existing research is used in other transition metal, such as platinum (II) (US9224963B2), palladium (II) (Chem.Sci.2016,7,6083) etc..The metal complex of this kind of quad-tree index also has preferable performance using upper in OLED.But in the gold (III) of equal electronic structures, this research field is just relatively upper less.Moreover, gold (III) complex of tridentate ligand is to need to use the compound of mercury as predecessor (Chem.Commun.2005,2906), this is harmful for environment in synthetic route.Golden (III) complex of four ring gears metallization can make complex more stable, increase the rigidity of molecule, keep luminous efficiency higher.In principle, golden (III) complex of four ring gears metallization, can not need to use mercury compound as predecessor in synthesis.

Summary of the invention

According to the various embodiments of the application, providing one kind has metal organic complex and its application, mixture, organic electronic device, solves the problems, such as one or more involved in background technique.

A kind of metal organic complex, shown in the structure of the metal organic complex such as general formula (1):

Wherein,

M is metallic atom, and M is selected from gold or palladium；

L is selected from two bridging bases；

Ar¹And Ar²Independently selected from the aromatic group with 5-20 annular atom, the miscellaneous aromatic group with 5-20 annular atom or the non-aromatic ring system with 5-20 annular atom；Ar¹And Ar²Independently there is substituent R¹Or R²；

Ar³And Ar⁴Independently with the aromatic group with 5-20 annular atom, the miscellaneous aromatic group with 5-20 annular atom or the non-aromatic ring system with 5-20 annular atom；Ar³And Ar⁴Independently there is substituent R³Or R⁴；

R¹、R²、R³And R⁴Independently selected from hydrogen, deuterium, halogen atom or the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom.

A kind of polymer, at least one repetitive unit includes above-mentioned metal organic complex in the polymer.

A kind of mixture, including at least one organic functional material and above-mentioned metal is organic or above-mentioned polymer；The organic functional material is selected from hole-injecting material, hole mobile material, electron transport material, electron injection material, electron-blocking materials, hole barrier materials, illuminator, material of main part or dopant material.

A kind of composition, the composition includes organic solvent and above-mentioned metal is organic or above-mentioned polymer or said mixture.

Above-mentioned metal is organic or above-mentioned polymer or said mixture or above-mentioned composition are preparing the application in organic electronic device.

A kind of organic electronic device includes above-mentioned metal organic complex or above-mentioned polymer or said mixture.

The details of one or more embodiments of the invention proposes in following attached drawing and description.Other features, objects, and advantages of the present invention will become obvious from specification, attached drawing and claims.

Specific embodiment

In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and do not have to It is of the invention in limiting.

Herein, composition, printing ink and ink have the same meaning, and can be interchanged between them.Herein, material of main part, host material, Host and Matrix material have the same meaning, and can be interchanged between them.Herein, metallo-organic complex, metal organic complex and organometallic complex have the same meaning, and can be interchanged.

Shown in the structure of the metal organic complex of one embodiment such as general formula (1):

Wherein,

M is metallic atom, and M is selected from gold or palladium；

L is selected from two bridging bases；

It should be noted that Ar¹、Ar²、Ar³And Ar⁴Independently when repeatedly occurring, it may be the same or different.R¹、R²、R³And R⁴Independently when repeatedly occurring, it may be the same or different.R¹、R²、R³And R⁴It can be connected in any position of aromatic rings or miscellaneous aromatic rings.

The metal organic complex is for that especially as luminescent layer dopant material, can provide higher device tuorbillion optical property and device lifetime in OLED.The metal organic complex of such structure novel includes to four coordinate bonds to metallic atom center, so that entire complex has better chemistry, light, electricity, thermal stability, and four coordinate bonds increase the rigidity of entire complex, therefore the tuorbillion optical property of complex material can be effectively improved, this provides possibility for the photoelectric properties and device stability for improving related device.And in synthetic route, do not need to use mercury compound as predecessor, therefore keep the process of synthesis simpler and environmentally friendly.In addition, being optimized by device architecture, change concentration of the metal complex in matrix, can reach optimal device performance, be easy to implement the OLED device of efficient high brightness high stable, preferable material options are provided to full-color display and illumination application.

M is selected from gold in one of the embodiments,.From the point of view of heavy atoms effect, golden (Au) is used as to the central metal M of above-mentioned metal organic complex.This is because gold is chemically stable, and there is significant heavy atoms effect can obtain high luminous efficiency.

For M in occurring each time, identical or different is a bridge or two bridges or three bridges or four bridging bases, it and Ar¹Or Ar²Or Ar³Or Ar⁴It is connected with singly-bound or double bond.

L is selected from the straight chained alkyl with 0-10 carbon atom, the branched alkyl with 0-10 carbon atom, the straight-chain alkenyl with 0-10 carbon atom, the branched-chain alkenyl with 0-10 carbon atom, the alkylether radicals with 0-10 carbon atom, O, S, S=O, SO in one of the embodiments,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, aromatic ring comprising 5-20 carbon atom or include 4-20 The heteroaromatic ring system of carbon atom；R is identical or different, selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom.

Further, R is selected from the miscellaneous aromatic ring of the aromatic ring comprising 5-15 carbon atom or 4-15 carbon atom.In one embodiment, R is selected from the miscellaneous aromatic ring of the aromatic ring comprising 5-10 carbon atom or 4-10 carbon atom.L is selected from the straight chained alkyl with 0-5 carbon atom, the branched alkyl with 0-5 carbon atom, the straight-chain alkenyl with 0-5 carbon atom, the branched-chain alkenyl with 0-5 carbon atom, the alkylether radicals with 0-5 carbon atom in one of the embodiments,.Further, L is selected from the straight chained alkyl with 0-2 carbon atom, the branched alkyl with 0-2 carbon atom, the straight-chain alkenyl with 0-2 carbon atom, the branched-chain alkenyl with 0-2 carbon atom, the alkylether radicals with 0-2 carbon atom.

L is selected from following any group in one of the embodiments:

Wherein, #1 is indicated and the Ar¹Any position bonding；#2 is indicated and the Ar²Any position bonding；Z contains at least one nitrogen, oxygen, carbon, silicon, boron, sulphur or phosphorus atoms；R¹⁸-R²⁰Independently selected from H, D, halogen atom, CN, NO₂、CF₃、B(OR)₂、Si(R)₃, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom；The R is selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, has 1-20 The branched alkyl of carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom.

L is selected from following any group in one of the embodiments,.

Wherein, R₃、R₄、R₅With R₆Definition and above-described R¹And R²It defines identical；Dotted line key indicates and Ar¹Or Ar²The key of bonding.

L is selected from following any group in one of the embodiments,.

Ar in one of the embodiments,¹、Ar²、Ar³Or Ar⁴Selected from including a non-aromatic ring system with 5-20 annular atom that is unsubstituted or being replaced by R.It has the triplet that metal complex can be improved, consequently facilitating obtaining the technical effect of green light or blue light emitters.

For the purpose of the present invention, non-aromatic ring system includes 1-10 carbon atom in ring system, and not only including saturation but also including the unsaturated cyclic annular system in part, they can be unsubstituted or by the single or multiple substitutions of group R, and group R can be same or different in occurring each time.Non-aromatic ring system includes 1-3 carbon atom in ring system in one of the embodiments,.Non-aromatic ring system can also include one or more hetero atoms in one of the embodiments,.Wherein, hetero atom can be selected from one of Si, N, P, O, S and Ge or a variety of.Hetero atom is selected from one of Si, N, P, O and S or a variety of in one of the embodiments,.These for example can be class cyclohexyl or class piperidines system, be also possible to class cyclo-octadiene ring-type system.The term is equally applicable to condensed non-aromatic ring system.Non-aromatic ring system includes 1-6 carbon atom in ring system in one of the embodiments,.

In one of the embodiments, R is selected from: (1) C1-C10 alkyl, wherein, C1-C10 alkyl can refer to following group: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, cyclobutyl, 2- methyl butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, suberyl, n-octyl, cyclooctyl, 2- ethylhexyl, trifluoromethyl, five methyl fluorides, 2, 2, 2- trifluoroethyl, vinyl, acrylic, cyclobutenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl group, heptenyl, cycloheptenyl, octenyl, cyclo-octene base, acetenyl, propinyl, butynyl, pentynyl, hexin base or octynyl；(2) C1-C10 alkoxy, wherein C1-C10 alkoxy can be with nail oxygroup, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2- methyl butoxy；(3) C2-C10 aryl or heteroaryl, depending on purposes, it can be monovalence or divalent, in each case can also be by the above-mentioned group R referred to¹⁰Replace and can be connect by any desired position with aromatic group or miscellaneous aromatic rings.In one of the embodiments, C2-C10 aryl or heteroaryl are selected from following group: benzene, naphthalene, anthracene, pyrene, dihydropyrene, it bends, Asia puecon, firefly anthracene, naphthacene, pentacene, BaP, furans, benzofuran, isobenzofuran, dibenzofurans, thiophene, benzothiophene, isothiophene, dibenzothiophen, pyrroles, indoles, iso-indoles, carbazole, pyridine, quinoline, isoquinolin, acridine, phenanthridines, benzo -5, 6- quinoline, benzo -6, 7- quinoline, benzo -7, 8- quinoline, phenthazine, phenoxazine, pyrazoles, indazole, imidazoles, benzimidazole, naphtho- imidazoles, phenanthro- imidazoles, pyridine-imidazole, pyrazine and imidazoles, quinoxaline and imidazoles, oxazole, benzoxazoles, aphthoxazoles, anthra oxazole, phenanthro- oxazole, isoxazole, 1, 2- thiazole, 1, 3- thiazole, benzothiazole, pyridazine, Benzo pyridazine, pyrimidine, benzo pyrimidine, quinoxaline, pyrazine, phenazine, 1,5- benzodiazine, nitrogen carbazole, benzo carboline, phenanthroline, 1,2,3- triazole, 1,2,4- triazole, benzotriazole, 1,2,3- oxadiazoles, 1,2,4- oxadiazoles, 1,2,5- oxadiazoles, 1,3,4- oxadiazoles, 1,2,3- thiadiazoles, 1,2,4- thiadiazoles, 1,2,5- thiadiazoles, 1,3,4- thiadiazoles, 1,3,5- triazine, 1,2,4- triazine, 1,2,3- triazine, tetrazolium, 1,2,4,5- tetrazine, 1,2,3,4- tetrazine, 1,2,3,5- tetrazine, purine, pteridine, indolizine or diazosulfide.For purposes of the present invention, fragrant and heteroaromatic ring system thinks especially in addition to the above-mentioned aryl and heteroaryl referred to, also refers to biphenylene, sub- terphenyl, fluorenes, two fluorenes of spiral shell, dihydro phenanthrene, tetrahydro pyrene and cis or trans indenofluorene.

Ar in one of the embodiments,¹、Ar²、Ar³And Ar⁴Independently selected from the aromatic group with 5-20 annular atom or the heteroaromatic group with 5-20 annular atom.Ar in one of the embodiments,¹、Ar²、Ar³And Ar⁴Independently selected from the aromatic group with 5-18 annular atom or the heteroaromatic group with 5-18 annular atom.Ar in one of the embodiments,¹、Ar²、Ar³And Ar⁴Independently selected from the aromatic group with 5-12 annular atom or the heteroaromatic group with 5-12 annular atom.Ar in one of the embodiments,¹、Ar²、Ar³And Ar⁴In at least one be selected from the heteroaromatic group comprising a ring hetero atom N.Further, Ar¹、Ar²、Ar³And Ar⁴In at least there are two be selected from the heteroaromatic group comprising a ring hetero atom N.

Aromatic group refers to the alkyl for containing at least one aromatic ring, including monocyclic groups and polycyclic loop system.Heteroaromatic group refers to the alkyl (containing hetero atom) comprising at least one hetero-aromatic ring, including monocyclic groups and polycyclic loop system.These polycyclic rings can be with With two or more rings, two of them carbon atom is shared by two adjacent rings, i.e. condensed ring.These polycyclic ring species, at least one is aromatics or heteroaromatic.For the purpose of the present invention, aromatic series or heteroaromatic ring system not only include the system of aromatic radical or heteroaryl perfume base, moreover, plurality of aryl or heteroaryl can also be interrupted (< 10% non-H atom, such as C, N or O atom) by short non-aromatic unit., two fluorenes of 9'- spiral shell, 9,9- diaryl fluorenes, triaryl amine, the systems such as diaryl ether, for the goal of the invention it also hold that being aromatic ring system.Excellent multiple aryl or heteroaryl can also be interrupted (the non-H atom less than 5%) by short non-aromatic unit in one of the embodiments,.

Specifically, aromatic group can be selected from benzene, naphthalene, anthracene, phenanthrene, perylene, aphthacene, pyrene, BaP, triphenylene, acenaphthene, fluorenes or their derivative.

Specifically, the example of heteroaromatic group can have: furans, benzofuran, thiophene, benzothiophene, pyrroles, pyrazoles, triazole, imidazoles, oxazole, oxadiazoles, thiazole, tetrazolium, indoles, carbazole, pyrrolo- imidazoles, pyrrolopyrrole, Thienopyrroles, thienothiophene, furans and pyrroles, furans and furans, thienofuran, benzo isoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinolin, cinnoline, quinoxaline, phenanthridines, primary pyridine, quinazoline, quinazolinone or their derivative.

Ar in one of the embodiments,¹-Ar⁴Independently selected from following any group:

Wherein, A¹-A⁸Independently selected from CR3 or N；

Y¹Selected from CR₄R₅、SiR₄R₅、NR₃, C (=O), S or O；

R₃、R₄、R₅Independently selected from H, D, straight chained alkyl with 1 to 20 C atom, alkoxy with 1 to 20 C atom, thio alkoxy group with 1 to 20 C atom, branch or cricoid alkyl with 3 to 20 C atoms, branch or cricoid alkoxy with 3 to 20 C atoms, branch or cricoid thio alkoxy group with 3 to 20 C atoms, branch or cricoid silyl-group with 3 to 20 C atoms, substituted keto group with 1 to 20 C atom, alkoxycarbonyl groups with 2 to 20 C atoms, aryloxycarbonyl group with 7 to 20 C atoms, cyano group, carbamoyl group, halogen formyl group, formyl group, isocyano group group, isocyanate groups, thiocyanates group, isothiocyanic acid Ester group, hydroxyl group, nitryl group, CF₃One of group, Cl, Br, F, crosslinkable group, the substituted or unsubstituted aromatics with 5 to 40 annular atoms or heteroaromatic ring system, the aryloxy group with 5 to 40 annular atoms or heteroaryloxy group are a variety of；R₃、R₄、R₅In at least one ring for being bonded with the building stone form monocycle or polycyclic aliphatic series or aromatic ring or R₃、R₄、R₅In at least two be mutually bonded to form monocycle or polycyclic aliphatic series or aromatic ring.

Ar in one of the embodiments,¹-Ar⁴Independently selected from following any group.Wherein, the H on ring can arbitrarily be replaced.

Ar in one of the embodiments,¹And Ar²Independently selected from following any group:

Wherein, P expression and Ar³Or Ar⁴Any position bonding；

X¹-X¹⁸Independently contain at least one nitrogen, oxygen, carbon, silicon, boron, sulphur or phosphorus atoms；

R⁵-R⁷Independently selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom；

Y is selected from two bridging bases.

Y is selected from the straight chained alkyl with 0-2 carbon atom, the branched alkyl with 0-2 carbon atom, the straight-chain alkenyl with 0-2 carbon atom, the branched-chain alkenyl with 0-2 carbon atom, the alkylether radicals with 0-2 carbon atom, O, S, S=O, SO in one of the embodiments,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, the aromatic ring comprising 5-20 carbon atom or the heteroaromatic ring system comprising 4-20 carbon atom.R is identical or different, selected from hydrogen, deuterium, halogen atom, hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom.

Y is selected from non-aromatic group in one of the embodiments, is selected from any group as cited by above-mentioned L.

Wherein, R⁸-R¹⁰Independently selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom.

Ar in one of the embodiments,³And Ar⁴Independently selected from following any group:

Wherein, Q is indicated and the Ar¹Or Ar²Any position bonding；

X¹⁹-X³¹Independently contain at least one nitrogen, oxygen, carbon, silicon, boron, sulphur or phosphorus atoms；

R¹¹-R¹³Independently selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom.

Wherein, R¹¹-R¹³Independently selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom.

The structure of metal organic complex such as general formula (I-1) or (I-18) are shown in one of the embodiments:

Wherein, R²¹-R³¹It is fragrant independently selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the heteroaryl with 1-20 carbon atom Group or non-aromatic ring system with 1-20 carbon atom；R²¹-R³¹It can be connected in any position of aromatic group or miscellaneous aromatic group；X³²-X³⁸Independently contain at least one nitrogen, oxygen, carbon, silicon, boron, sulphur or phosphorus atoms.

X in one of the embodiments³²-X³⁸In at least one be selected from nitrogen-atoms.

The specific example of suitable metal organic complex according to the invention is given below, but not limited to this.

Metal organic complex according to the invention is luminescent material in one of the embodiments, and emission wavelength is 300 between 1000nm.Further, the emission wavelength of the metal organic complex is 350 between 900nm.The emission wavelength of metal organic complex is 400 between 800nm in one of the embodiments,.What is herein referred to luminous refers to luminescence generated by light or electroluminescent.Photoluminescence efficiency >=30% of metal organic complex in one of the embodiments,.Photoluminescence efficiency >=40% of metal organic complex in one of the embodiments,.Photoluminescence efficiency >=50% of metal organic complex in one of the embodiments,.Photoluminescence efficiency >=60% of metal organic complex in one of the embodiments,.

Metal organic complex according to the invention is also possible to non-luminescent material in one of the embodiments,.

The application of above-mentioned metal organic complex in the polymer.The application of above-mentioned metal organic complex in the mixture.Application in above-mentioned metal organic complex organic electronic device.

The polymer of one embodiment, wherein at least one repetitive unit include above-mentioned metal organic complex.The polymer is non-conjugated highpolymer in one of the embodiments, wherein the structural unit as shown in general formula (1) is on side chain.In another embodiment, which is conjugated highpolymer.

The mixture of one embodiment includes at least one organic functional material and above-mentioned metal organic complex.Organic functional material is selected from hole (also referred to as electric hole) injection or transmission material (HIM/HTM), hole barrier materials (HBM), electron injection or transmission material (EIM/ETM), electron-blocking materials (EBM), organic host material (Host), singlet emitters (fluorescent illuminant), weight state illuminator (phosphorescent emitter) or organic thermal excitation delayed fluorescence material (TADF material).Organic thermal excitation delayed fluorescence material can be luminescent organometallic complex compound.Such as various organic functional materials are described later in detail in WO2010135519A1, US2009 0134784A1 and WO 2011110277A1, the full content in this three patent documents is incorporated herein by reference hereby.Organic functional material can be small molecule or high polymer material.

It is not polymer, oligomer, the molecule of dendritic or blend that term " small molecule " as defined herein, which refers to,.In particular, there is no repetitive structure in small molecule.Molecular weight≤3000 gram/mol of small molecule.Further molecular weight≤2000 gram/mol of small molecule.Further, molecular weight≤1500 gram/mol of small molecule.

High polymer, i.e. Polymer include homopolymer (homopolymer), copolymer (copolymer), block copolymer (block copolymer).In addition in the present invention, high polymer also includes tree (dendrimer), synthesis and application in relation to tree refer to [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH&Co.KGaA, 2002, Ed.George R.Newkome, Charles N.Moorefield, Fritz Vogtle.].

Conjugated highpolymer (conjugated polymer) is a high polymer, its main chain (backbone) is mainly made of the sp2 hybridized orbit of C atom, famous example has: polyacetylene polyacetylene and poly (phenylene vinylene), C atom on its main chain can also be replaced by other non-C atoms, and as the sp on main chain²When hydridization is interrupted by some natural defects, it is still considered as being conjugated highpolymer.In addition in the present invention conjugated highpolymer also include include arylamine (aryl amine), aryl hydrogen phosphide (aryl phosphine) and other heterocyclic arenes (heteroarmotics), metallo-organic complex (organometallic complexes) etc. on main chain.

The content of metal organic complex is 0.01 to 30wt% in one of the embodiments,.In one of the embodiments, the content of metal organic complex is 0.1 to 20wt%.The content of metal organic complex is 0.2 in one of the embodiments, To 20wt%.The content of metal organic complex is 2 to 15wt% in one of the embodiments,.

In one of the embodiments, which includes above-mentioned metal organic complex and a kind of triplet host material.At this point, metal organic complex is as object (phosphorescent emitter), weight percent≤30wt% of metal organic complex.Weight percent≤20wt% of metal organic complex in one of the embodiments,.Further, weight percent≤15wt% of metal organic complex.

In one of the embodiments, which includes the triplet emitters of above-mentioned metal organic complex, a kind of triplet host material and another kind.

In one of the embodiments, which includes above-mentioned metal organic complex and a kind of hot activation delayed fluorescence luminescent material (TADF).

Some more detailed descriptions (but not limited to this) are made to triplet host material, triplet emitters and TADF material below.1. triplet material of main part (Triplet Host):

The example of triplet material of main part is not particularly limited, and any metal complex or organic compound may all be used as main body, as long as its triplet energy ratio illuminator, especially triplet emitters or phosphorescent emitter are higher.The example that can be used as the metal complex of triplet main body (Host) includes but is not limited to following general structure:

M is metal；(Y³-Y⁴) it is one liang of tooth ligand, Y³And Y⁴Independently selected from C, N, O, P or S；L is an assistant ligand；M is an integer, value from 1 to this metal maximum coordination number；M+n is the maximum coordination number of this metal.

The metal complex that can be used as triplet main body in one of the embodiments, has following form:

Wherein, (O-N) is one liang of tooth ligand, wherein metal and O and N Atomic coordinate.

M is selected from Ir or Pt in one of the embodiments,.

The example of the organic compound of triplet main body be can be used as selected from the compound for including aromatic hydrocarbon ring base, such as benzene, biphenyl, triphenyl, benzo, fluorenes；It or include the compound of fragrant heterocyclic radical, such as dibenzothiophenes, dibenzofurans, dibenzo selenophen, furans, thiophene, benzofuran, benzothiophene, benzo selenophen, carbazole, indole carbazole, pyridine indoles, two pyridine of pyrroles, pyrazoles, imidazoles, triazole type, oxazole, thiazole, oxadiazoles, dislike triazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazines, oxazines, dislike thiazine, oxadiazines, indoles, benzimidazole, indazole, oxazole, dibenzo oxazole, benzisoxazole, benzothiazole, quinoline, isoquinolin, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, phenthazine, phenoxazine, benzofuran pyridine, furopyridine, benzothiophene pyridine, thiophene pyridine, two pyridine of benzo selenophen pyridine and selenophen benzo；It or include the group of 2 to 10 ring structures, they can be the aromatic hydrocarbon ring group or aromatic heterocycle group of identical or different type, and link together directly with one another or by least one group below, such as oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, boron atom, chain structural unit and aliphatic cyclic group.Wherein, each Ar can be further substituted, and substituent group is selected from hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkyl, aryl or heteroaryl.

In one of the embodiments, triplet material of main part is selected from the compound comprising at least one following group:

Wherein, R¹-R⁷Independently selected from hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkyl, aryl or heteroaryl, when they are aryl or heteroaryl, they and above-mentioned Ar¹And Ar²Meaning is identical；N is selected from 0,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20；X1-X8 is selected from CH or N, X⁹Selected from CR¹R²Or NR¹。

The example of suitable triplet material of main part is listed in following table.

2, triplet emitters (Triplet Emitter)

Triplet emitters are also referred to as phosphorescent light-emitting materials.In a preferential embodiment, triplet emitters are that have formula M₂(L) metal complex of n.Wherein M₂It is a metallic atom；It can be identical or different when L occurs every time, be an organic ligand, it passes through, and one or more positions are bonded or coordination is connected on metallic atom M；N is an integer greater than 1, and preferably choosing is 1,2,3,4,5 or 6.These metal complexes are connected on a polymer by one or more positions in one of the embodiments, preferably by organic ligand.

In one of the embodiments, metallic atom M₂Selected from transition metal element or lanthanide series or actinides.M is selected from Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag in one of the embodiments,.M is selected from Os, Ir, Ru, Rh, Re, Pd or Pt in one of the embodiments,.

Triplet emitters include cheland in one of the embodiments, i.e. ligand, are coordinated by least two binding sites and metal.Triplet emitters include two or three identical or different bidentates or multidentate ligand in one of the embodiments,.Cheland is conducive to improve the stability of metal complex.

The example of organic ligand is selected from phenylpyridine derivative, 7,8- benzoquinoline derivative, 2 (2- thienyl) pyridine derivates, 2 (1- naphthalene) pyridine derivates or 2 phenylchinoline derivatives.All these organic ligands may be all substituted, such as be replaced by fluorine-containing or trifluoromethyl.Assistant ligand can be selected from acetic acid acetone or picric acid.

In a preferential embodiment, the metal complex that can be used as triplet emitters has following form:

Wherein M is metal, is selected from transition metal element, lanthanide series or actinides.

Ar¹For cyclic group, identical or different, and Ar can be when occurring every time¹Including at least there is a donor atom, that is, there is the atom of a lone pair electrons, such as nitrogen or phosphorus, is connected by its cyclic group and metal coordination；Ar²For cyclic group, identical or different, Ar can be when occurring every time²Including at least there is a C atom, it is connect by its cyclic group with metal；Ar¹And Ar²It is linked together by covalent bond, can respectively carry one or more substituent groups, they can also be linked together by substituent group again；It can be identical or different when L occurs every time, L is assistant ligand, is preferable over double-tooth chelate ligand, preferably monoanionic, bidentate cheland；M is selected from 1,2 or 3；N is selected from 0,1 or 2.L is double-tooth chelate ligand in one of the embodiments,.L is monoanionic, bidentate cheland in one of the embodiments,.M is 2 or 3 in one of the embodiments,.M is 3 in one of the embodiments,.N is 0 or 1 in one of the embodiments,.N is 0 in one of the embodiments,.

The example that the material of some triplet emitters is extremely applied can be found in following patent documents and document: 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 2010099 852, WO 2010102709, US 20070087219A1, US 20090061681A1, US 20010053462A1, Baldo, Thompson et al.Nature 403, (2000), 750-753, US 20090061681A1, US 20090061681A1, Adachi et al.Appl.Phys.Lett.78 (2001), 1622-1624, J.Kido et al.Appl.Phys.Lett.65 (1994), 2124, Kido et al.Chem.L Ett.657,1990, US 2007/0252517A1, 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 20010053462A1, WO 2007095118A1, US 2012004407A1, WO 2012007088A1, WO2012007087A1, WO 201 2007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1.The full content in the above-mentioned patent document and document listed is incorporated herein by reference hereby.

The example of some suitable triplet emitters is listed in following table.

3, TADF material

Traditional organic fluorescence materials can only be shone using 25% singlet exciton to be formed is electrically excited, and the internal quantum efficiency of device is lower (up to 25%).Although phosphor material passes through between being since the strong SO coupling in heavy atom center enhances, it can efficiently use and be electrically excited the singlet exciton to be formed and Triplet exciton, the internal quantum efficiency of device is made to reach 100%.But phosphor material is expensive, and stability of material is poor, and device efficiency the problems such as serious of roll-offing limits its application in OLED.Hot activation delayed fluorescence luminescent material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.Such material generally has small singlet-triplet poor (Δ Est), triplet excitons can by it is counter be between pass through be transformed into singlet exciton shine.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation.Device internal quantum efficiency can reach 100%.Material structure is controllable simultaneously, and property is stablized, cheap woth no need to noble metal, in having a extensive future for the field OLED.

TADF material needs to have lesser singlet-triplet poor.Δ Est < 0.3eV in one of the embodiments,.Δ Est < 0.2eV in one of the embodiments,.Δ Est < 0.1eV in one of the embodiments,.TADF material has smaller Δ Est in one of the embodiments,.In another embodiment, TADF has preferable fluorescence quantum efficiency.Some TADF luminous material can be found in following patent documents: 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.Le Tt., 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., 48,2012,9 580, 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.J.Mater.Chem.C., 1,2013,4599, Adachi, et.al.J.Phys.C Hem.A., 117,2013,5607, the full content in the above-mentioned patent listed or article file is incorporated herein by reference hereby.

The example of some suitable TADF luminescent materials is listed in following table.

The metal organic complex is for being deposited type OLED device in one of the embodiments,.At this point, molecular weight≤1000g/mol of the metal organic complex.Molecular weight≤900g/mol of metal organic complex in one of the embodiments,.Molecular weight≤850g/mol of metal organic complex in one of the embodiments,.Molecular weight≤800g/mol of metal organic complex in one of the embodiments,.Molecular weight≤700g/mol of metal organic complex in one of the embodiments,.

The metal organic complex is used for printed form OLED in one of the embodiments,.At this point, molecular weight >=700g/mol of the metal organic complex.Molecular weight >=800g/mol of metal organic complex in one of the embodiments,.Molecular weight >=900g/mol of metal organic complex in one of the embodiments,.Molecular weight >=1000g/mol of metal organic complex in one of the embodiments,.Molecular weight >=1100g/mol of metal organic complex in one of the embodiments,.

Above-mentioned metal organic complex in one of the embodiments, solubility >=5mg/ml at 25 DEG C, in toluene.Solubility >=8mg/ml in toluene in one of the embodiments,.Solubility >=10mg/ml in toluene in one of the embodiments,.

The mixture of another embodiment includes above-mentioned polymer, and described in the mixture about an embodiment as above such as the various components of the mixture and content, details are not described herein.

The composition of one embodiment includes organic solvent and above-mentioned metal organic complex or polymer or mixture.In the present embodiment, composition is ink.When being used for printing technology to the composition, the viscosity of ink, surface tension is important parameter.The surface tension parameter of suitable ink is suitable for specific substrate and specific printing process.Further, the present invention provide it is a kind of from solution preparation include metal organic complex or polymer according to the invention film.

In one embodiment, ink operating temperature or in the surface tension at 25 DEG C in 19dyne/cm to 50dyne/cm range.In one of the embodiments, ink operating temperature or in the surface tension at 25 DEG C in 22dyne/cm to 35dyne/cm range.In one of the embodiments, ink operating temperature or in the surface tension at 25 DEG C in 25dyne/cm to 33dyne/cm range.

In one embodiment, viscosity of the ink at operating temperature or 25 DEG C is in 1cps to 100cps range.In one of the embodiments, ink in the viscosity at operating temperature or 25 DEG C viscosity of the ink at operating temperature or 25 DEG C in one of the embodiments, in 1cps to 50cps range.Viscosity of the ink at operating temperature or 25 DEG C is in 1.5cps to 20cps range in one of the embodiments,.Viscosity of the ink at operating temperature or 25 DEG C is in 4.0cps to 20cps range in one of the embodiments,.The ink jet printing so that the composition is more convenient for.

Viscosity can be adjusted by different methods, as chosen the concentration with functional material in ink by suitable solvent.It include that the ink of metal organic complex or high polymer can facilitate people that will print ink to adjust according to printing process used in range appropriate.The weight ratio for the organic functional material for including in composition is 0.3%~30wt%.Composition in one of the embodiments, In include organic functional material weight ratio be 0.5%~20wt%.The weight ratio for the organic functional material for including in composition in one of the embodiments, is 0.5%~15wt%.The weight ratio for the organic functional material for including in composition in one of the embodiments, is 0.5%~10wt%.The weight ratio for the organic functional material for including in composition in one of the embodiments, is 1%~5wt%.

In one embodiment, organic solvent includes the first solvent, which is selected from based on aromatics and/or heteroaromatic solvent.Further, which can be aliphatic chain/cyclosubstituted arsol or aromatics ketone solvent or aromatic ether solvents.

The example of first solvent has, but it is not limited to: based on aromatics or heteroaromatic solvent: to diisopropyl benzene, penta benzene, naphthane, cyclohexyl benzene, chloronaphthalene, 1, 4- dimethylnaphthalene, 3- isopropyl biphenyl, p-Methylisopropylbenzene, diamyl benzene, 3 penta benzene, amyl toluene, ortho-xylene, meta-xylene, paraxylene, adjacent diethylbenzene, NSC 62102, p-Diethylbenzene, 1, 2, 3, 4- durene, 1, 2, 3, 5- durene, 1, 2, 4, 5- durene, butylbenzene, detergent alkylate, dihexyl benzene, dibutyl benzene, to diisopropyl benzene, 1- methoxynaphthalene, cyclohexyl benzene, dimethylnaphthalene, 3- isopropyl biphenyl, p-Methylisopropylbenzene, 1- methyl naphthalene, 1, 2, 4- trichloro-benzenes, 1, 3- dipropoxy benzene, 4, 4- difluoro-diphenylmethane, 1, 2- dimethoxy-4 ' (1- acrylic) benzene, diphenyl-methane, 2- phenylpyridine, 3- phenylpyridine, N- methyldiphenylamine, 4- isopropyl biphenyl, α, α-dichloro diphenyl methane, 4- (3- phenyl propyl) pyridine, Ergol, 1, bis- (3,4- 3,5-dimethylphenyl) ethane of 1-, 2- isopropyl naphthalene, benzyl ether etc.；Solvent based on ketone: 1-tetralone, 2- tetralone, 2- (phenyl epoxy) tetralone, 6- (methoxyl group) tetralone, acetophenone, propiophenone, benzophenone and their derivative, such as 4- methyl acetophenone, 3- methyl acetophenone, 2- methyl acetophenone, 4- methyl phenyl ketone, 3- methyl phenyl ketone, 2- methyl phenyl ketone, isophorone, 2,6,8- trimethyl -4- nonanone, fenchone, methyl n-heptyl ketone, 3- nonanone, butyl ketone, 2- decanone, 2,5- acetyl butyryl, phorone, two n-pentyl ketone；Aromatic ether solvents: 3- phenoxytoluene, butyl phenyl ether, benzyl butyl benzene, p-anisaldehyde dimethyl-acetal, tetrahydro -2- phenoxy group -2H- pyrans, 1, 2- dimethoxy-4 '-(1- acrylic) benzene, 1, 4- benzdioxan, 1, 3- dipropyl benzene, 2, 5- dimethoxy-p, this ether of 4- ethyl, 1, 2, 4- trimethoxy-benzene, 4- (1- acrylic) -1, 2- dimethoxy benzene, 1, 3- dimethoxy benzene, glycidyl phenyl ether, dibenzyl ether, 4- tert-butyl anisole, trans--anethole, 1, 2- dimethoxy benzene, 1- methoxynaphthalene, diphenyl ether, 2- phenoxy group methyl ether, 2- phenoxy group tetrahydrofuran, ethyl -2- naphthyl ether, amyl ether c hexyl ether, dioctyl ether, butyl cellosolve, diethylene glycol diethyl Ether, diethylene glycol butyl methyl ether, dibutyl ethylene glycol ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether；Ester solvent: sad alkyl ester, decanedioic acid alkyl ester, stearic acid alkyl ester, benzoic acid alkyl esters, phenylacetic acid alkyl ester, cinnamic acid alkyl ester, oxalic acid alkyl ester, maleic acid alkyl ester, alkane lactone, oleic acid alkyl ester etc..

Further, which is also selected from aliphatic ketone, for example, methyl n-heptyl ketone, 3- nonanone, butyl ketone, 2- decanone, 2,5- acetyl butyryl, 2,6,8- trimethyl -4- nonanones, phorone, two n-pentyl ketone etc.；Or fatty ether, for example, one of amyl ether, hexyl ether, dioctyl ether, butyl cellosolve, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, dibutyl ethylene glycol ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether and tetraethyleneglycol dimethyl ether or a variety of.

In one embodiment, the organic solvent further includes the second solvent, second solvent is selected from methanol, ethyl alcohol, 2-methyl cellosolve, methylene chloride, chloroform, chlorobenzene, o-dichlorohenzene, tetrahydrofuran, methyl phenyl ethers anisole, morpholine, toluene, ortho-xylene, meta-xylene, paraxylene, 1, 4 dioxanes, acetone, methyl ethyl ketone, 1, 2 dichloroethanes, 3- phenoxytoluene, 1, 1, 1- trichloroethanes, 1, 1, 2, 2- tetrachloroethanes, ethyl acetate, butyl acetate, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, naphthane, one of naphthalane and indenes are a variety of.

In one embodiment, the composition can be solution or suspension.This is determined according to the compatibility between organic mixture and organic solvent.

Purposes of the above-mentioned composition as coating or printing ink when preparing organic electronic device, particularly preferably passes through the preparation method of printing or coating.

Wherein, suitable printing or coating technique include but is not limited to inkjet printing, spray printing (Nozzle Printing), typographic printing, silk-screen printing, dip-coating, rotary coating, blade coating, roller printing, reverse roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brushing or bat printing or the coating of slit-type squash type etc..Preferably intaglio printing, spray printing and ink jet printing.The composition can also include component example, and lid component example is selected from one of surface active cpd, lubricant, wetting agent, dispersing agent, hydrophobing agent and bonding agent or a variety of, so as to which for adjusting viscosity, filming performance improves adhesion etc..Related printing technique, and its to the related request in relation to solution, such as solvent and concentration, viscosity etc., details refer to " print media handbook: technology and production method " (Handbook of Print Media:Technologies of Helmut Kipphan chief editor and Production Methods),ISBN 3-540-67326-1。

In one embodiment, the application of above-mentioned metal organic complex or polymer in organic electronic device.The organic electronic device can be selected from Organic Light Emitting Diode (Organic Light-Emitting Diode, OLED), organic photovoltaic battery (Organic Photovoltage, OPV), organic light emission battery (OLEEC), organic field-effect tube (organic field2effect transistor, OFET), organic light-emitting field effect pipe, organic laser, organic spin electric device, organic sensor or organic plasmon emitting diode (Organic Plasmon Emitting Diode).In one embodiment, organic electronic device OLED.Further, which is used for the luminescent layer of OLED.

The organic electronic device of one embodiment includes at least one above-mentioned metal organic complex or polymer or mixture.Wherein, organic electronic device may include cathode, anode and the functional layer between cathode and anode, which includes that above-mentioned transition metal complex or above-mentioned polymer or said mixture or the functional layer are prepared by above-mentioned composition.Specifically, organic electronic device includes at least cathode, anode and a functional layer between cathode and anode, functional layer includes at least a kind of above-mentioned organic compound or above-mentioned polymer or above-mentioned organic mixture or the functional layer is prepared by above-mentioned composition.Functional layer is selected from the one or more of hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer, electron transfer layer, electronic barrier layer and luminescent layer.

The organic electronic device can be selected from Organic Light Emitting Diode (Organic Light-Emitting Diode, OLED), organic photovoltaic battery (Organic Photovoltage, OPV), organic light emission battery (OLEEC), organic field-effect tube (organic field2effect transistor, OFET), organic light-emitting field effect pipe, organic laser, organic spin electric device, organic sensor or organic plasmon emitting diode (Organic Plasmon Emitting Diode).In one embodiment, which is organic electroluminescence device, such as OLED.

In one embodiment, OLED includes the substrate stacked gradually, anode, luminescent layer and cathode.Wherein, the number of plies of luminescent layer is at least one layer.

Substrate can be opaque or transparent.Transparent substrate can be used to manufacture a transparent light emitting component, refer to the Nature such as Bulovic 1996,380, p29 and Gu etc., Appl.Phys.Lett.1996, and 68, p2606.Substrate can be rigid or elasticity.Substrate is also possible to plastics, metal, semiconductor wafer or glass.Preferably, substrate has smooth surface.Substrate free of surface defects is especially desirable selection.In an embodiment, substrate is flexible, optional in thin polymer film or plastics, and glass transition temperature Tg is 150 DEG C or more.Flexible base board can be poly- (ethylene glycol terephthalate) (PET) or polyethylene glycol (2,6- naphthalene) (PEN).The glass transition temperature Tg of substrate is 200 DEG C or more in one of the embodiments,.The glass transition temperature Tg of substrate is 250 DEG C or more in one of the embodiments,.The glass transition temperature Tg of substrate is 300 DEG C or more in one of the embodiments,.

Anode may include conductive metal or metal oxide or conducting polymer.Anode can be easily injected into hole into hole injection layer (HIL) or hole transmission layer (HTL) or luminescent layer.In one embodiment, the absolute value of the difference of the HOMO energy level or valence-band level of the illuminator in the work function and luminescent layer of anode or the p-type semiconductor material as HIL or HTL or electronic barrier layer (EBL) is less than 0.5eV.The absolute value of the difference of the HOMO energy level or valence-band level of illuminator in the work function and luminescent layer of anode or the p-type semiconductor material as HIL or HTL or electronic barrier layer (EBL) is less than 0.3eV.The absolute value of the difference of the HOMO energy level or valence-band level of illuminator in the work function and luminescent layer of anode or the p-type semiconductor material as HIL or HTL or electronic barrier layer (EBL) is less than 0.2eV.The example of anode material includes but is not limited to: Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO and aluminium-doped zinc oxide (AZO) etc..Anode material can also be with other materials.Any suitable technology deposition, such as a suitable physical vaporous deposition, including rf magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) etc. can be used in anode material.In other embodiments, anode is patterning.Patterned ITO electrically-conductive backing plate is commercially available, and can be used to prepare the organic electronic device according to the present embodiment.

Cathode may include conductive metal or metal oxide.Cathode can be easily injected into electronics to EIL or ETL or directly into luminescent layer.In one embodiment, the absolute value of the difference of the lumo energy or conduction level of illuminator or the n-type semiconductor as electron injecting layer (EIL) or electron transfer layer (ETL) or hole blocking layer (HBL) is less than 0.5eV in the work function of cathode and luminescent layer.The absolute value of the difference of the lumo energy or conduction level of illuminator or the n-type semiconductor as electron injecting layer (EIL) or electron transfer layer (ETL) or hole blocking layer (HBL) is less than 0.3eV in the work function and luminescent layer of cathode.The absolute value of the difference of the lumo energy or conduction level of illuminator or the n-type semiconductor as electron injecting layer (EIL) or electron transfer layer (ETL) or hole blocking layer (HBL) is less than 0.2eV in the work function and luminescent layer of cathode.The material of all cathodes that can be used as OLED all may be as the cathode material of the organic electronic device of the present embodiment.The example of cathode material includes but is not limited to: Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO etc..Any suitable technology deposition, such as a suitable physical vaporous deposition, including rf magnetron sputtering, vacuum thermal evaporation and electron beam (e-beam) etc. can be used in cathode material.

OLED can also include other function layer, such as hole injection layer (HIL), hole transmission layer (HTL), electronic barrier layer (EBL), electron injecting layer (EIL), electron transfer layer (ETL), hole blocking layer (HBL).It is described in front suitable for the material in these functional layers.

In one of the embodiments, in luminescent device according to the invention, luminescent layer includes a kind of metal organic complex according to the invention or polymer, which can be prepared by the method that vacuum evaporation or solution are processed.

In one embodiment, the emission wavelength of the organic electroluminescence device luminescent device is 300 between 1000nm.The emission wavelength of organic electroluminescence device luminescent device is 350 between 900nm in one of the embodiments,.The emission wavelength of organic electroluminescence device luminescent device is 400 between 800nm in one of the embodiments,.

In one embodiment, the application of above-mentioned organic electronic device in the electronic device.Electronic equipment is selected from display equipment, lighting apparatus, light source or sensor.Wherein, organic electronic device can be organic electroluminescence device.

A kind of electronic equipment, including above-mentioned organic electronic device.

Below in conjunction with preferred embodiment, the present invention is described, but the present invention is not limited to the following examples, it should be understood that, appended claims summarise the scope of the present invention under the guidance of present inventive concept it should be appreciated by one skilled in the art that, to certain change that various embodiments of the present invention are carried out, will all be covered by the spirit and scope of claims of the present invention.

1, metal organic complex and its energy-structure

Metal organic complex Au-1, the energy level of Au-2, Au-3, Au-4 can be calculated by quantum, for example using TD-DFT (time-depentent DFT) by Gaussian03W (Gaussian Inc.), specific analogy method can be found in WO2011141110.Semi-empirical approach " Ground State/Hartree-Fock/Default Spin/LanL2MB " (Charge 0/Spin Singlet) Lai Youhua molecular geometry is used first, and then the energy-structure of organic molecule calculates " TD-SCF/DFT/Default Spin/B3PW91/gen geom=connectivity pseudo=lanl2 " (Charge 0/Spin Singlet) by TD-DFT (time-depentent DFT) method.HOMO and lumo energy are calculated according to following calibration equation, and S1 and T1 are directly used.

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

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

Wherein HOMO (G) and LUMO (G) is the direct calculated result of Gaussian 03W, unit Hartree.As a result as shown in Table 1.

Table one

2, the synthesis of metal organic complex

Embodiment 1: synthetic compound Au-1

Synthetic intermediate A:

In the atmosphere full of nitrogen, 3- bromobenzaldehyde (16g is placed in the three-necked flask of a 500mL, 1eq) and o-phenylenediamine (10.28g, 1eq), acetonitrile (300mL) and 37% hydrochloride aqueous solution (30mL, 3.5eq) are then added thereto, then under ice bath (0 DEG C), it is slowly added dropwise 30% aqueous hydrogen peroxide solution (68mL, 7eq), stirs 4 hours.Then it is mixed with a large amount of water (1000mL), solid is filtered, obtain brown solid intermediate A, yield 90%.

Synthetic intermediate B:

In the atmosphere full of nitrogen, 6- bromo-2-pyridyl carboxylic acid (17.5g is placed in the three-necked flask of a 500mL, 1eq) and o-phenylenediamine (10.28g, 1eq), acetonitrile (300mL) and 37% hydrochloride aqueous solution (30mL, 3.5eq) are then added thereto, then under ice bath (0 DEG C), it is slowly added dropwise 30% aqueous hydrogen peroxide solution (68mL, 7eq), stirs 4 hours.Then it is mixed with a large amount of water (1000mL), solid is filtered, obtain brown solid intermediate B, yield 65%.

Synthetic intermediate C:

Intermediate A (1.50g, 1eq), aniline (1.03g, 2eq), Pd are placed in the three-necked flask of a 250mL₂(dba)₃(0.5g, 0.1eq), X-Phos (0.24g, 0.1eq) and sodium tert-butoxide (5.31g, 10eq), repetition is vacuumized and is filled three times with nitrogen, and toluene (120mL) then is added thereto, is heated to 120 DEG C and is stirred 4 hours.Then vacuum distillation removes solvent, water (250mL) and methylene chloride (250mL) extraction is added, take lower layer's organic solution, vacuum distillation concentration, then silica gel is crossed by the mixed solvent of the ethyl acetate of ratio and petroleum ether of 1:5, takes most components, fraction is concentrated under reduced pressure, obtain brown solid intermediate C, yield 25%.

Synthetic intermediate D:

Intermediate B (1.80g, 1eq), intermediate C (1.88g, 2eq), Pd are placed in the three-necked flask of a 100mL₂(dba)₃(0.6g, 0.1eq), X-Phos (0.29g, 0.1eq) and sodium tert-butoxide (6.33g, 10eq), repetition is vacuumized and is filled three times with nitrogen, and toluene (60mL) then is added thereto, is heated to 120 DEG C and is stirred 24 hours.Then vacuum distillation removes solvent, water (250mL) and methylene chloride (250mL) extraction is added, take lower layer's organic solution, vacuum distillation concentration, then silica gel is crossed by the mixed solvent of the ethyl acetate of ratio and petroleum ether of 1:5, takes most components, fraction is concentrated under reduced pressure, obtain brown solid intermediate D, yield 20%.

Synthetic compound Au-1:

In the atmosphere full of nitrogen, intermediate D (0.3g, 1eq), KAuCl are placed in the three-necked flask of a 100mL₄.2H2O (0.29g, 1.1eq) and potassium carbonate (0.61g, 10eq) are then added methanol (30mL) thereto, are stirred at room temperature 12 hours.Then vacuum distillation removes solvent, methylene chloride extraction is added, take lower layer's organic solution, vacuum distillation concentration, then crosses silica gel, extracting yellow component than the mixed solvent of petroleum ether using 1:5 as the methylene chloride of ratio, fraction is concentrated under reduced pressure, it is recrystallized by the way that ethyl alcohol is added in right amount, obtains the complex Au-1 of yellow green, yield 35%.

Embodiment 2: synthetic compound Au-2

Synthetic intermediate E:

In the atmosphere full of nitrogen, 1,3- dibromobenzene (15g, 1eq), Pd (PPh are placed in the three-necked flask of a 1000mL₃)₄(1.46g, 0.02eq) and potassium carbonate (35g, 4eq), then toluene (200mL) is added and water (100mL) is solvent, and it is heated to 120 DEG C, then toluene (150mL) solution of 2- boric acid indoles (16g, 0.8eq) is added dropwise thereto, is then stirred 24 hours at 120 DEG C.Then it mixes, extract upper organic layer and is concentrated under reduced pressure with a large amount of water (1000mL), then cross silica gel by the mixed solvent of the ethyl acetate of ratio and petroleum ether of 1:10, take most components, fraction is concentrated under reduced pressure, brown solid intermediate E, yield 88% are obtained.

Synthetic intermediate F:

In the atmosphere full of nitrogen, 2,6- dibromo pyridine (15g, 1eq), Pd (PPh are placed in the three-necked flask of a 1000mL₃)₄(1.46g, 0.02eq) and potassium carbonate (35g, 4eq), then toluene (200mL) is added and water (100mL) is solvent, and it is heated to 120 DEG C, then toluene (150mL) solution of 2- boric acid indoles (16g, 0.8eq) is added dropwise thereto, is then stirred 24 hours at 120 DEG C.Then it mixes, extract upper organic layer and is concentrated under reduced pressure with a large amount of water (1000mL), then cross silica gel by the mixed solvent of the ethyl acetate of ratio and petroleum ether of 1:5, take most components, fraction is concentrated under reduced pressure, brown solid intermediate F, yield 69% are obtained.

Synthetic intermediate G:

Intermediate E (1.50g, 1eq), aniline (1.03g, 2eq), Pd are placed in the three-necked flask of a 250mL₂(dba)₃(0.5g, 0.1eq), X-Phos (0.24g, 0.1eq) and sodium tert-butoxide (5.31g, 10eq), repetition is vacuumized and is filled three times with nitrogen, and toluene (120mL) then is added thereto, is heated to 120 DEG C and is stirred 4 hours.Then vacuum distillation removes solvent, water (250mL) and methylene chloride (250mL) extraction is added, take lower layer's organic solution, vacuum distillation concentration, then silica gel is crossed by the mixed solvent of the ethyl acetate of ratio and petroleum ether of 1:5, takes most components, fraction is concentrated under reduced pressure, obtain brown solid intermediate G, yield 22%.

Synthetic intermediate H:

Intermediate F (1.80g, 1eq), intermediate G (1.88g, 2eq), Pd are placed in the three-necked flask of a 100mL₂(dba)₃(0.6g, 0.1eq), X-Phos (0.29g, 0.1eq) and sodium tert-butoxide (6.33g, 10eq), repetition is vacuumized and is filled three times with nitrogen, and toluene (60mL) then is added thereto, is heated to 120 DEG C and is stirred 24 hours.Then vacuum distillation removes solvent, water (250mL) and methylene chloride (250mL) extraction is added, take lower layer's organic solution, vacuum distillation concentration, then silica gel is crossed by the mixed solvent of the ethyl acetate of ratio and petroleum ether of 1:5, takes most components, fraction is concentrated under reduced pressure, obtain brown solid intermediate H, yield 26%.

Synthetic compound Au-2:

In the atmosphere full of nitrogen, intermediate H (0.3g, 1eq), KAuCl are placed in the three-necked flask of a 100mL₄.2H2O (0.29g, 1.1eq) and potassium carbonate (0.61g, 10eq) are then added methanol (30mL) thereto, are stirred at room temperature 12 hours.Then vacuum distillation removes solvent, methylene chloride extraction is added, take lower layer's organic solution, vacuum distillation concentration, then crosses silica gel, extracting yellow component than the mixed solvent of petroleum ether using 1:5 as the methylene chloride of ratio, fraction is concentrated under reduced pressure, it is recrystallized by the way that ethyl alcohol is added in right amount, obtains the complex Au-2 of yellow, yield 30%.

Embodiment 3: synthetic compound Au-3

Synthetic intermediate I:

In the atmosphere full of nitrogen, 3- hydroxy benzaldehyde (10.56g is placed in the three-necked flask of a 500mL, 1eq) and o-phenylenediamine (10.28g, 1eq), acetonitrile (300mL) and 37% hydrochloride aqueous solution (30mL, 3.5eq) are then added thereto, then under ice bath (0 DEG C), it is slowly added dropwise 30% aqueous hydrogen peroxide solution (68mL, 7eq), stirs 4 hours.Then it is mixed with a large amount of water (1000mL), solid is filtered, obtain brown solid intermediate compound I, yield 86%.

Synthetic intermediate J:

In the atmosphere full of nitrogen, 6- bromo-2-pyridyl carboxylic acid (17.5g is placed in the three-necked flask of a 500mL, 1eq) and o-phenylenediamine (10.28g, 1eq), acetonitrile (300mL) and 37% hydrochloride aqueous solution (30mL, 3.5eq) are then added thereto, then under ice bath (0 DEG C), it is slowly added dropwise 30% aqueous hydrogen peroxide solution (68mL, 7eq), stirs 4 hours.Then it is mixed with a large amount of water (1000mL), solid is filtered, obtain brown solid intermediate J, yield 67%.

Synthetic intermediate K:

Intermediate compound I (5.00g, 1eq), intermediate J (7.82g, 1.2eq), Cs are placed in the three-necked flask of a 100mL₂CO₃(7.75g, 1eq) and Cu (0.3g, 0.2eq), repetition are vacuumized and are filled three times with nitrogen, and DMF (5mL) then is added thereto, is heated to 140 DEG C and stirs 24 hours.Then water (250mL) and methylene chloride (250mL) extraction is added, take lower layer's organic solution, vacuum distillation concentration, then silica gel is crossed by the mixed solvent of the ethyl acetate of ratio and petroleum ether of 1:3, take most components, fraction is concentrated under reduced pressure, brown solid intermediate K, yield 34% are obtained.

Synthetic compound Au-3:

In the atmosphere full of nitrogen, intermediate K (0.26g, 1eq), KAuCl are placed in the three-necked flask of a 100mL₄.2H₂O (0.29g, 1.1eq) and potassium carbonate (0.61g, 10eq) are then added methanol (30mL) thereto, are stirred at room temperature 12 hours.Then vacuum distillation removes solvent, methylene chloride extraction is added, take lower layer's organic solution, vacuum distillation concentration, then crosses silica gel, extracting yellow component than the mixed solvent of petroleum ether using 1:5 as the methylene chloride of ratio, fraction is concentrated under reduced pressure, it is recrystallized by the way that ethyl alcohol is added in right amount, obtains lurid compound Au-3, yield 32%.

Embodiment 4: synthetic compound Au-4

Synthetic intermediate L:

In the atmosphere full of nitrogen, m -bromoacetophenone (10.56g, 1eq), 2- boric acid indoles (16g, 0.8eq), Pd (PPh are placed in the three-necked flask of a 1000mL₃)₄(1.46g, 0.02eq) and potassium carbonate (35g, 4eq), is then added toluene (400mL) and water (100mL) is solvent, and is heated to 120 DEG C and stirs 24 hours.Then it mixes, extract upper organic layer and is concentrated under reduced pressure with a large amount of water (1000mL), then cross silica gel by the mixed solvent of the ethyl acetate of ratio and petroleum ether of 1:10, take most components, fraction is concentrated under reduced pressure, brown solid intermediate L, yield 82% are obtained.

Synthetic intermediate M:

In the atmosphere full of nitrogen, 2,6- dibromo pyridine (15g, 1eq), Pd (PPh are placed in the three-necked flask of a 1000mL₃)₄(1.46g, 0.02eq) and potassium carbonate (35g, 4eq), then toluene (200mL) is added and water (100mL) is solvent, and it is heated to 120 DEG C, then toluene (150mL) solution of 2- boric acid indoles (16g, 0.8eq) is added dropwise thereto, is then stirred 24 hours at 120 DEG C.Then it mixes, extract upper organic layer and is concentrated under reduced pressure with a large amount of water (1000mL), then cross silica gel by the mixed solvent of the ethyl acetate of ratio and petroleum ether of 1:5, take most components, fraction is concentrated under reduced pressure, brown solid intermediate M, yield 64% are obtained.

Synthetic intermediate N:

Intermediate L (5.00g, 1eq), intermediate M (7.82g, 1.2eq), Cs are placed in the three-necked flask of a 100mL₂CO₃(7.75g, 1eq) and Cu (0.3g, 0.2eq), repetition are vacuumized and are filled three times with nitrogen, and DMF (5mL) then is added thereto, is heated to 140 DEG C and stirs 24 hours.Then water (250mL) and methylene chloride (250mL) extraction is added, take lower layer's organic solution, vacuum distillation concentration, then silica gel is crossed by the mixed solvent of the ethyl acetate of ratio and petroleum ether of 1:3, take most components, fraction is concentrated under reduced pressure, brown solid intermediate N, yield 36% are obtained.

Synthetic compound Au-4:

In the atmosphere full of nitrogen, intermediate N (0.26g, 1eq), KAuCl are placed in the three-necked flask of a 100mL₄.2H₂O (0.29g, 1.1eq) and potassium carbonate (0.61g, 10eq) are then added methanol (30mL) thereto, are stirred at room temperature 12 hours.Then vacuum distillation removes solvent, methylene chloride extraction is added, take lower layer's organic solution, vacuum distillation concentration, then crosses silica gel, extracting yellow component than the mixed solvent of petroleum ether using 1:5 as the methylene chloride of ratio, fraction is concentrated under reduced pressure, it is recrystallized by the way that ethyl alcohol is added in right amount, obtains lurid compound Au-4, yield 30%.

3, the photophysical property of complex

As shown in Figure 1, it can be seen that the emission spectrum maximum peak of gold (III) complex of tetradentate ligands class is all located at 500 to electronic device of the complex suitable for yellow light between 700nm, illustrating this type from the solid PL spectrum of Au-1.

4, the preparation and characterization of OLED device

With ITO/NPD (60nm)/15%Au-1:mCP (45nm)/TPBi (35nm)/LiF (1nm)/Al (150nm)/cathode The preparation step of OLED device is as follows:

A, the cleaning of electro-conductive glass substrate: for the first time in use, can be cleaned with multi-solvents, such as chloroform, ketone, isopropanol are cleaned, and then carry out UV ozone plasma treatment；

B, HTL (60nm), EML (45nm), ETL (35nm): in high vacuum (1 × 10^-6Millibar, mbar) in hot evaporation form；

C, cathode: LiF/Al (1nm/150nm) is in high vacuum (1 × 10^-6Millibar) in hot evaporation form；

D, encapsulate: device is encapsulated in nitrogen glove box with ultraviolet hardening resin.

Current Voltage brightness (JVL) characteristic of OLED device is characterized by characterization equipment, while recording important parameter such as efficiency and external quantum efficiency.Through detecting, the maximum external quantum efficiency of OLED device Au-1 is respectively 5.4%.

OLED device structure can also advanced optimize, and such as HTM, the Combinatorial Optimization of ETM and material of main part will further improve the performance of device, especially efficiency, driving voltage and service life.

Claims

A kind of metal organic complex, which is characterized in that shown in the structure of the metal organic complex such as general formula (1):

Wherein,

M is metallic atom, and M is selected from gold or palladium；

L is selected from two bridging bases；

Ar¹And Ar²Independently selected from the aromatic group with 5-20 annular atom, the miscellaneous aromatic group with 5-20 annular atom or the non-aromatic ring system with 5-20 annular atom；Ar¹And Ar²Independently there is substituent R¹Or R²；

Ar³And Ar⁴Independently with the aromatic group with 5-20 annular atom, the miscellaneous aromatic group with 5-20 annular atom or the non-aromatic ring system with 5-20 annular atom；Ar³And Ar⁴Independently there is substituent R³Or R⁴；

R¹、R²、R³And R⁴Independently selected from hydrogen, deuterium, halogen atom or the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom.
Metal organic complex according to claim 1, which is characterized in that the Ar¹And Ar²Independently selected from following any group:

Wherein, P expression and Ar³Or Ar⁴Any position bonding；

X¹-X¹⁸Independently contain at least one nitrogen, oxygen, carbon, silicon, boron, sulphur or phosphorus atoms；

R⁵-R⁷Independently selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom；

Y is selected from two bridging bases.
Metal organic complex according to claim 1 or 2, which is characterized in that the Ar¹And Ar²Independently selected from following any group:

Wherein, R⁸-R¹⁰Independently selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom.
Metal organic complex according to any one of claim 1 to 3, which is characterized in that the Ar³And Ar⁴Independently selected from following any group:

Wherein, Q is indicated and the Ar¹Or Ar²Any position bonding；

X¹⁹-X³¹Independently contain at least one nitrogen, oxygen, carbon, silicon, boron, sulphur or phosphorus atoms；

R¹¹-R¹³Independently selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom.
The metal organic complex according to any one of right 1 to 4, which is characterized in that the Ar³And Ar⁴Independently selected from following any group:

Wherein, R¹¹-R¹³Independently selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom.
Metal organic complex according to any one of claim 1 to 5, which is characterized in that the L is selected from following any group:

Wherein, #1 is indicated and the Ar¹Any position bonding；#2 is indicated and the Ar²Any position bonding；Z contains at least one nitrogen, oxygen, carbon, silicon, boron, sulphur or phosphorus atoms；R¹⁸-R²⁰Independently selected from H, D, halogen atom, CN, NO₂、CF₃、B(OR)₂、Si(R)₃, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom；The R is selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom.
Metal organic complex according to any one of claim 1 to 6, which is characterized in that the structure of the metal organic complex such as general formula (I-1) or (I-2) are shown:

Wherein, R²¹、R²²、R²³And R²⁴Independently selected from hydrogen, deuterium, halogen atom, the straight chained alkyl with 1-20 carbon atom, the branched alkyl with 1-20 carbon atom, the straight-chain alkenyl with 1-20 carbon atom, the branched-chain alkenyl with 1-20 carbon atom, the alkylether radicals with 1-20 carbon atom, the aromatic group with 1-20 carbon atom, the miscellaneous aromatic group with 1-20 carbon atom or the non-aromatic ring system with 1-20 carbon atom；X³²-X³⁷Independently contain at least one nitrogen, oxygen, carbon, silicon, boron, sulphur or phosphorus atoms.
Metal organic complex according to claim 7, which is characterized in that the metal organic complex is selected from one of complex as shown in general formula:
A kind of polymer, which is characterized in that at least one repetitive unit includes such as metal organic complex of any of claims 1-8 in the polymer.
A kind of mixture, which is characterized in that the mixture includes at least one organic functional material and such as metal organic complex of any of claims 1-8 or polymer as claimed in claim 9；The organic functional material is selected from hole-injecting material, hole mobile material, electron transport material, electron injection material, electron-blocking materials, hole barrier materials, illuminator, material of main part or dopant material.
A kind of composition, which is characterized in that the composition includes organic solvent and such as metal organic complex of any of claims 1-8 or polymer as claimed in claim 9 or mixture as claimed in claim 10.
Metal organic complex according to claim 1 to 8 or polymer as claimed in claim 9 or mixture described in any one of claim 10 or composition as claimed in claim 11 are preparing the application in organic electronic device.
A kind of organic electronic device, which is characterized in that comprising such as metal organic complex described in any item of the claim 1 to 8 or polymer as claimed in claim 9 or mixture as claimed in claim 10.
Organic electronic device according to claim 13, it is characterized in that, the organic electronic device is selected from Organic Light Emitting Diode, organic photovoltaic battery, organic light emission battery, organic field-effect tube, organic light-emitting field effect pipe, organic laser, organic spin electric device, organic sensor or organic plasmon emitting diode.