CN106397406A - Aromatic heterocyclic derivative and preparing method thereof and inorganic electroluminescence device - Google Patents

Aromatic heterocyclic derivative and preparing method thereof and inorganic electroluminescence device Download PDF

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CN106397406A
CN106397406A CN201610793032.0A CN201610793032A CN106397406A CN 106397406 A CN106397406 A CN 106397406A CN 201610793032 A CN201610793032 A CN 201610793032A CN 106397406 A CN106397406 A CN 106397406A
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CN106397406B (en
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高春吉
崔敦洙
王永光
张成成
孙向南
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention discloses an aromatic heterocyclic derivative. The derivative has a structure shown as the formula (I). Compared with the prior art, the provided aromatic heterocyclic derivative is prepared by introducing Q1, Q2, Ar1, Ar2, Ar3 and Ar4 groups into a pyridino- [3.4-g] aromatic heterocyclic derivative, electronic intensity and skills can be improved, and meanwhile, R1 can improve properties of the aromatic heterocyclic derivative, therefore, an inorganic electroluminescence device of the aromatic heterocyclic derivative containing the formula (I) has high luminance, long service life and high efficiency. The formula (I) is shown in the specification.

Description

A kind of heteroaromatic derivative and preparation method thereof and a kind of organic electroluminescence device
The application is on 06 02nd, 2015 for the applying date, Application No. 201510295963.3, and invention and created name is The divisional application of " a kind of heteroaromatic derivative and preparation method thereof and a kind of organic electroluminescence device ".
Technical field
The present invention relates to organic photoelectrical material technical field, more particularly, to a kind of heteroaromatic derivative and preparation method thereof with And a kind of organic electroluminescence device.
Background technology
Organic electroluminescence device (OLED) is a kind of new flat panel display device, typically by two opposed electrodes and It is inserted at least one of which organic luminescent compounds composition between this two electrodes.Electric charge is injected between the anode and cathode In the organic layer being formed, to form electronics and hole pair, make the organic compound with fluorescence or phosphorescent characteristics create light and send out Penetrate.
Organic electroluminescence device due to have energy-conservation, fast response time, colour stable, environmental suitability strong, radiationless, The features such as light weight, thickness of thin, with developing rapidly of photoelectric communication in recent years and MultiMedia Field, organic optoelectronic material is Become the core of modern society's information and electronic industry.But, the research in this field still has some key issues not obtain very Just solve, device lifetime is short, luminous efficiency is low becomes its wide variety of bottleneck of restriction.
Content of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of heteroaromatic derivative and preparation method thereof with And a kind of organic electroluminescence device, had higher luminous by organic electroluminescence device prepared by described heteroaromatic derivative Efficiency and longer life-span.
The invention provides a kind of heteroaromatic derivative, there is structure shown in formula (I)：
Wherein,
L1、L2、L3、L4Independent selected from 0 or 1；
Q1And Q2Independent selected from nitrogen, oxygen, sulphur, the aryl of carbon number 6～30 or carbon number 1～30 heterocyclic radical；
R1It is 1～30 alkyl, substituted or unsubstituted carbon number 6～50 selected from hydrogen atom, cyano group, carbon number Aryl, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, the aromatic series of substituted or unsubstituted carbon number 7～30 The aralkyl of amido, the aralkoxy of substituted or unsubstituted carbon number 7～30 or substituted or unsubstituted carbon number 7～30 Sulfydryl；
Ar1、Ar2、Ar3、Ar4Independent selected from hydrogen atom, the aralkyl of substituted or unsubstituted carbon number 7～50, take The aralkoxy of generation or unsubstituted carbon number 7～50, the aralkyl sulfydryl of substituted or unsubstituted carbon number 7～50, carbon The aryl of atomicity 6～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, substituted or unsubstituted carbon number 7 ～30 aromatic series amido.
Preferably, described heteroaromatic derivative has following structure：
Wherein,
Z1～Z16Independent selected from CH, C or N；
L3And L4Independent selected from 0 or 1；
R1It is 1～30 alkyl, substituted or unsubstituted carbon number 6～50 selected from hydrogen atom, cyano group, carbon number Aryl, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, the aromatic series of substituted or unsubstituted carbon number 7～30 The aralkyl of amido, the aralkoxy of substituted or unsubstituted carbon number 7～30 or substituted or unsubstituted carbon number 7～30 Sulfydryl；
Ar1、Ar2、Ar3、Ar4Independent selected from hydrogen atom, the aralkyl of substituted or unsubstituted carbon number 7～50, take The aralkoxy of generation or unsubstituted carbon number 7～50, the aralkyl sulfydryl of substituted or unsubstituted carbon number 7～50, carbon The aryl of atomicity 6～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, substituted or unsubstituted carbon number 7 ～30 aromatic series amido.
Preferably, in described heteroaromatic derivative ,-R1Selected from following structure：
-O-R1'；-S-R1'；
Wherein,
Z1～Z8Independent selected from CH, C or N；
R'1And R'2Independent selected from carbon number be 1～30 alkyl, the aryl of carbon number 6～50, replacement or do not take The heterocyclic radical of carbon number 5～50 in generation or the aromatic series amido of substituted or unsubstituted carbon number 6～30.
Preferably, in described heteroaromatic derivative ,-Ar1、-Ar2、-Ar3、-Ar4Independent selected from following formula (1)～formula (35) structure shown in：
Wherein,
X and Y independence selected from hydrogen atom, halogen atom, cyano group, the alkyl of substituted or unsubstituted carbon number 1～30, The alkoxyl of substituted or unsubstituted carbon number 1～30, the thiazolinyl of substituted or unsubstituted carbon number 2～30, replacement or The aralkyl of unsubstituted carbon number 7～30, the aralkoxy of substituted or unsubstituted carbon number 7～30, replacement or not The aryl of carbon number 6～30 that replaces, the aryloxy group of substituted or unsubstituted carbon number 6～30, substituted or unsubstituted The aromatic series amido of the heterocyclic radical of carbon number 5～30 or substituted or unsubstituted carbon number 7～30.
Preferably, work as Q1And Q2It is all phenyl, R1During for cyano group or phenyl, Ar1And Ar2Independent selected from replacing or unsubstituted The aryl of carbon number 7～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50 or substituted or unsubstituted carbon The aromatic series amido of atomicity 7～30.
Preferably, L1And L2It is asynchronously 0.
Present invention also offers a kind of preparation method of heteroaromatic derivative, including：
Compound shown in formula (III) is reacted with the compound shown in the compound shown in formula (IV) and formula (V), Obtain the heteroaromatic derivative shown in formula (I)；
Wherein,
X ' is halogen atom, Y ' and Y1' independent selected from B (OH)2Or H；
L1、L2、L3、L4Independent selected from 0 or 1；
Q1And Q2Independent selected from nitrogen, oxygen, sulphur, the aryl of carbon number 6～30 or carbon number 1～30 heterocyclic radical；
R1It is 1～30 alkyl, substituted or unsubstituted carbon number 6～50 selected from hydrogen atom, cyano group, carbon number Aryl, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, the aromatic series of substituted or unsubstituted carbon number 7～30 The aralkyl of amido, the aralkoxy of substituted or unsubstituted carbon number 7～30 or substituted or unsubstituted carbon number 7～30 Sulfydryl；
Ar1、Ar2、Ar3、Ar4Independent selected from hydrogen atom, the aralkyl of substituted or unsubstituted carbon number 7～50, take The aralkoxy of generation or unsubstituted carbon number 7～50, the aralkyl sulfydryl of substituted or unsubstituted carbon number 7～50, carbon The aryl of atomicity 6～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, substituted or unsubstituted carbon number 7 ～30 aromatic series amido.
Present invention also offers a kind of organic electroluminescence device, including above-mentioned heteroaromatic derivative or above-mentioned preparation method The heteroaromatic derivative of preparation.
Preferably, above-mentioned organic electroluminescence device includes first electrode, second electrode and is arranged at described first electrode Organic matter layer and second electrode between；Described organic matter layer include above-mentioned heteroaromatic derivative or above-mentioned preparation method preparation Heteroaromatic derivative.
Present invention also offers a kind of organic photoelectrical material, including the heteroaromatic described in claim 1～6 any one The heteroaromatic compounds of the preparation method preparation described in compound or claim 7；Described organic photoelectrical material includes organic sun Battery, Electronic Paper, Organophotoreceptor or organic transistor.
Compared with prior art, the invention provides a kind of heteroaromatic derivative, there is structure shown in formula (I), wherein, L1、L2、L3、L4Independent selected from 0 or 1；Q1And Q2Independent selected from nitrogen, oxygen, sulphur, the aryl of carbon number 6～30 or carbon atom The heterocyclic radical of number 1～30；R1It is 1～30 alkyl, substituted or unsubstituted carbon atom selected from hydrogen atom, cyano group, carbon number The aryl of number 6～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, substituted or unsubstituted carbon number 7～30 Aromatic series amido, the aralkoxy of substituted or unsubstituted carbon number 7～30 or substituted or unsubstituted carbon number 7～ 30 aralkyl sulfydryl；Ar1、Ar2、Ar3、Ar4The independent aralkyl selected from hydrogen atom, substituted or unsubstituted carbon number 7～50 Base, the aralkoxy of substituted or unsubstituted carbon number 7～50, the aralkyl mercapto of substituted or unsubstituted carbon number 7～50 Base, the aryl of carbon number 6～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, substituted or unsubstituted carbon are former The aromatic series amido of subnumber 7～30.Compared with prior art, the heteroaromatic derivative that the present invention provides is in pyrido [3,4- G] introduce Q in heteroaromatic derivative1、Q2、Ar1、Ar2、Ar3With Ar4Group, can improve electronics closeness and technical ability, meanwhile, R1Can To improve the performance of heteroaromatic derivative, so that comprising the organic electroluminescence device of the heteroaromatic derivative shown in formula (I) Possesses the features such as higher brightness, preferable heat resistance, long-life and high efficiency.
Specific embodiment
The invention provides a kind of heteroaromatic derivative, there is structure shown in formula (I)：
Wherein,
L1、L2、L3、L4Independent selected from 0 or 1；
Q1And Q2Independent selected from nitrogen, oxygen, sulphur, the aryl of carbon number 6～30 or carbon number 1～30 heterocyclic radical；
R1It is 1～30 alkyl, substituted or unsubstituted carbon number 6～50 selected from hydrogen atom, cyano group, carbon number Aryl, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, the aromatic series of substituted or unsubstituted carbon number 7～30 The aralkyl of amido, the aralkoxy of substituted or unsubstituted carbon number 7～30 or substituted or unsubstituted carbon number 7～30 Sulfydryl；
Ar1、Ar2、Ar3、Ar4Independent selected from hydrogen atom, the aralkyl of substituted or unsubstituted carbon number 7～50, take The aralkoxy of generation or unsubstituted carbon number 7～50, the aralkyl sulfydryl of substituted or unsubstituted carbon number 7～50, carbon The aryl of atomicity 6～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, substituted or unsubstituted carbon number 7 ～30 aromatic series amido.
The heteroaromatic derivative that the present invention provides is introducing Q in pyrido [3,4-g] heteroaromatic derivative1、Q2、Ar1、 Ar2、Ar3With Ar4Group, can improve electronics closeness and technical ability, meanwhile, R1The performance of heteroaromatic derivative can be improved, thus The organic electroluminescence device comprising the heteroaromatic derivative shown in formula (I) is made to possess higher brightness, preferable heat resistance, length The features such as life-span and high efficiency.
In heteroaromatic derivative shown in formula (I) provided by the present invention, described L1、L2、L3With L4Independent selected from 0 or 1, Preferably L1、L2、L3With L4It is asynchronously 0；It is furthermore preferred that L1、L2It is asynchronously 0；In some embodiments of the invention, L1、L2It is 1, L3With L4Independent selected from 0 or 1.
Q1And Q2Independent selected from nitrogen, oxygen, sulphur, the aryl of carbon number 6～30 or carbon number 1～30 heterocyclic radical；Excellent Elect nitrogen, oxygen, the heterocyclic radical of sulphur, the aryl of carbon number 6～24 or carbon number 1～24 as；More preferably nitrogen, oxygen, sulphur, carbon are former The aryl of subnumber 6～14 or the heterocyclic radical of carbon number 1～14.
In the present invention, preferably work as Q1And Q2It is all phenyl, R1During for cyano group or phenyl, Ar1And Ar2Independent selected from replacing or The aryl of unsubstituted carbon number 7～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50 or replacement or do not take The aromatic series amido of the carbon number 7～30 in generation.
Currently preferred, described heteroaromatic derivative has following arbitrary structures：
Wherein,
Z1～Z16Independent selected from CH, C or N.
R1It is 1～30 alkyl, substituted or unsubstituted carbon number 6～50 selected from hydrogen atom, cyano group, carbon number Aryl, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, the aromatic series of substituted or unsubstituted carbon number 7～30 The aralkyl of amido, the aralkoxy of substituted or unsubstituted carbon number 7～30 or substituted or unsubstituted carbon number 7～30 Sulfydryl；Be preferably hydrogen atom, cyano group, carbon number be 1～15 alkyl, the virtue of substituted or unsubstituted carbon number 6～14 Base, the heterocyclic radical of substituted or unsubstituted carbon number 5～14, the aromatic amine of substituted or unsubstituted carbon number 7～14 The aralkyl mercapto of base, the aralkoxy of substituted or unsubstituted carbon number 7～14 or substituted or unsubstituted carbon number 7～14 Base.
In the present invention, R1It is more preferably H, that is, described heteroaromatic ring derivative has following arbitrary structures：
In the present invention, R1It is also preferably following arbitrary structures：
-O-R1'；-S-R1'；
That is, described heteroaromatic derivative has following arbitrary structures：
Wherein,
Z1～Z8Independent selected from CH, C or N；
R'1And R'2Independent selected from carbon number be 1～30 alkyl, the aryl of carbon number 6～50, replacement or do not take The heterocyclic radical of carbon number 5～50 in generation or the aromatic series amido of substituted or unsubstituted carbon number 6～30；More preferably carbon Atomicity be 1～15 alkyl, the aryl of carbon number 6～30, the heterocyclic radical of substituted or unsubstituted carbon number 5～30 or The aromatic series amido of substituted or unsubstituted carbon number 6～15；In some embodiments of the invention, R1Selected from following Group：Phenyl, pyridine radicals, quinolyl, Phen base, N, N- diphenyl amido, pyridin-4-yl epoxide, pyridin-4-yl sulfydryl Or C5～C15 alkyl.
L3、L4、R1、Ar1、Ar2、Ar3、Ar4With above-mentioned L3、L4、R1、Ar1、Ar2、Ar3、Ar4Scope identical, here is no longer Repeat.
In the present invention, Ar1、Ar2、Ar3、Ar4Independent selected from hydrogen atom, substituted or unsubstituted carbon number 7～50 Aralkyl, the aralkoxy of substituted or unsubstituted carbon number 7～50, the virtue of substituted or unsubstituted carbon number 7～50 Alkane sulfydryl, the aryl of carbon number 6～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, substituted or unsubstituted The aromatic series amido of carbon number 7～30.More preferably hydrogen atom, the aralkyl of substituted or unsubstituted carbon number 7～30, The aralkoxy of substituted or unsubstituted carbon number 7～30, the aralkyl sulfydryl of substituted or unsubstituted carbon number 7～30, The aryl of carbon number 6～30, the heterocyclic radical of substituted or unsubstituted carbon number 5～30, substituted or unsubstituted carbon atom The aromatic series amido of number 7～14.In some embodiments of the invention, Ar1、Ar2、Ar3、Ar4Independent selected from following formula (1) structure shown in～formula (35)：
In the present invention, above-mentioned substituted aryl, replace heterocyclic radical, replace aromatic series amido, replace aralkoxy, In the aralkyl sulfydryl replacing, the aralkyl replacing, the thiazolinyl replacing, the aryloxy group of replacement, described substituted referring to containing substituted Base, described substituent is preferably selected from halogen, the alkyl of C1～C30, the thiazolinyl of C2～C30, the alkynyl of C2～C30, hydroxyl, C1 The alkoxyl of～C30, amino, nitro, sulfydryl, thioether group, imido grpup, cyano group, amide groups, phosphonate radical, phosphine, carboxyl, thio carbonyl Base, sulfonyl, sulfamoyl, carbonyl, aldehyde radical, ester group, acetyl group, acetoxyl group, carbamoyl, oxo base (=O), halo Alkyl, replace aminoacyl and aminoalkyl, cycloalkyl (can for monocyclic, fused polycycle or non-condensed polycyclic), heterocyclic radical (can be Monocyclic, fused polycycle or non-condensed are polycyclic), monocyclic or condense or non-condensed polyaromatic is (as phenyl, naphthyl, pyrrole radicals, indoles Base, furyl, thienyl, imidazole radicals, oxazolyl, isoxazolyl, thiazolyl, triazolyl, tetrazole radical, pyrazolyl, quinolyl, different Quinolyl, acridinyl, pyrazinyl, pyridazinyl, pyrimidine radicals, benzimidazolyl, benzothienyl or benzofuranyl), amino ,- The alkyl of O-C1～C20, O- aryl, aryl, the aryl-C1～alkyl of C20 ,-CO2CH3、-CONH2、-OCH2CONH2、-NH2、- SO2NH2、-OCHF2、-CF3、-OCF3.The substituent that these substituents are optionally selected from above-mentioned group further replaces.This In invention, described substituent is more preferably selected from the arbitrary substituent in following formula 36～65：
Present invention also offers a kind of preparation method of heteroaromatic derivative, including：
Compound shown in formula (III) is reacted with the compound shown in the compound shown in formula (IV) and formula (V), Obtain the heteroaromatic derivative shown in formula (I)；
Wherein,
X ' is halogen atom, Y ' and Y1' independent selected from B (OH)2Or H；
L1、L2、L3、L4Independent selected from 0 or 1；
Q1And Q2Independent selected from nitrogen, oxygen, sulphur, the aryl of carbon number 6～30 or carbon number 1～30 heterocyclic radical；
R1It is 1～30 alkyl, substituted or unsubstituted carbon number 6～50 selected from hydrogen atom, cyano group, carbon number Aryl, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, the aromatic series of substituted or unsubstituted carbon number 7～30 The aralkyl of amido, the aralkoxy of substituted or unsubstituted carbon number 7～30 or substituted or unsubstituted carbon number 7～30 Sulfydryl；
Ar1、Ar2、Ar3、Ar4Independent selected from hydrogen atom, the aralkyl of substituted or unsubstituted carbon number 7～50, take The aralkoxy of generation or unsubstituted carbon number 7～50, the aralkyl sulfydryl of substituted or unsubstituted carbon number 7～50, carbon The aryl of atomicity 6～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, substituted or unsubstituted carbon number 7 ～30 aromatic series amido.
Wherein, described L1、L2、L3、L4、Q1、Q2、Ar1、Ar2、Ar3、Ar4With R1All same as above, will not be described here.
The present invention is not particularly limited to the source of above-mentioned reaction raw materials, can prepare for commercially available being alternatively.The present invention Described in the compound shown in formula (III) be preferably prepared in accordance with the following methods：
In the present invention, work as Q1Or Q2During the heterocyclic radical of the aryl for C6～C30 or C1～C30, Y ' or Y1' it is B (OH)2, formula (III) compound shown in is carried out under catalyst action with the compound shown in the compound shown in formula (IV) or formula (V) Suzuki coupling reaction, described reaction condition is reaction condition well known to those skilled in the art, has no special restriction.
When described Q1 or Q2 is N, O or S, Y ' or Y1' it is H, now, shown in the compound shown in formula (III) and formula (IV) Compound or formula (V) shown in compound enter line replacement reaction；The condition of described displacement reaction is that those skilled in the art are ripe The conditions of replacement reaction known, has no special restriction.
In above-mentioned reaction equation, described R1, X ' all same as above, will not be described here.
In the present invention, when Y ＇ is B (OH)2When, the compound shown in described formula (IV) is preferably prepared in accordance with the following methods：
X ＂ is halogen atom.
Work as Y1' it is B (OH)2When, the compound shown in formula (V), preferably prepare in accordance with the following methods：
X ＂ is halogen atom.
In the present invention, as described L1With L2When being 0, the compound reduction shown in formula (III) be can get formula (I) simultaneously Shown compound.
The heteroaromatic derivative preparation method that the present invention provides simple it is easy to industrialization.
Present invention also offers a kind of organic electroluminescence device, including the heteroaromatic derivative shown in above-mentioned formula (I).
Described organic electroluminescence device is organic electroluminescence device well known to those skilled in the art, the present invention Preferably include first electrode, second electrode and the organic matter layer being arranged between described first electrode and second electrode；Described have Machine nitride layer comprises above-mentioned heteroaromatic derivative.
In the present invention, described organic matter layer refers to whole between organic electroluminescence device first electrode and second electrode Layer.At least one of which in described organic matter layer is luminescent layer.
According to the present invention, described organic matter layer preferably include hole injection layer, hole transmission layer, not only possessed hole injection but also Possess hole transport technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and both possessed Electric transmission, but also with one or more layers in electron injection technical ability layer, more preferably includes hole injection layer, the sky setting gradually Cave transport layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and electron injecting layer or the both tools setting gradually The injection of standby hole but also with hole transport technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer and not only possessed electric transmission but also Possesses electron injection technical ability layer.
When organic matter layer of the present invention comprises hole injection layer, hole transmission layer or has both possessed hole injection but also with hole biography During defeated technical ability layer, preferably described hole injection layer, hole transmission layer or both possessed hole inject but also with hole transport technical ability layer Middle at least one of which comprises hole injecting material, hole transporting material or had both possessed the thing but also with hole transport technical ability for the hole injection Matter.
When organic matter layer of the present invention is single layer structure, described organic matter layer is luminescent layer, when described organic matter layer is many During Rotating fields, described organic matter layer includes luminescent layer；Phosphorescence host is preferably included, fluorescent host, phosphorescence are mixed in described luminescent layer One or more of miscellaneous material and fluorescence dopant material；Described phosphorescence host, fluorescent host, phosphorescence dopant material and fluorescence are mixed One or more of miscellaneous material is the heteroaromatic derivative shown in formula (I).
Described luminescent layer is preferably also red, yellow or cyan luminescent layer, and described heteroaromatic derivative is red, yellow Or the main body of cyan luminescent layer or dopant.As, when described luminescent layer is cyan luminescent layer, the virtue shown in described formula (I) Hete rocyclic derivatives are when adulterating for cyan main body or cyan, it is possible to provide high efficiency, high brightness, high-resolution and long-life have Machine luminescent device.
When described organic matter layer includes electron transfer layer, described electron transfer layer may include the heteroaromatic shown in formula (I) Derivative and/or metallic compound.Described metallic compound is the material for electric transmission well known to those skilled in the art , have no special restriction.
When described organic matter layer includes luminescent layer with electron transfer layer simultaneously, described luminescent layer can divide with electron transfer layer Do not include the heteroaromatic derivative shown in formula (I) that structure is identical or differs.
The organic electroluminescence device that the present invention provides, using the heteroaromatic derivative shown in formula (I) and conventional material system Become, the present invention to the preparation method of described organic electroluminescence device and is not limited, this area conventional method, this Bright preferably by methods such as film vapor deposition, electron beam evaporation or physical vapour deposition (PVD)s on substrate evaporation metal and there is electric conductivity Oxide and their alloy formed anode, be then formed on organic matter layer and evaporation cathode, obtain organic electroluminescence and send out Optical device.
Described organic matter layer can include above-mentioned hole injection layer, hole transmission layer, luminescent layer, hole blocking layer simultaneously And the sandwich construction of electron transfer layer, and these sandwich constructions can be according to above-mentioned film vapor deposition, electron beam evaporation or physics gas The mutually method such as deposition evaporation, it is possible to use various macromolecular material solvent engineering substitutes evaporation coating method, such as spin-coating (spin-coating), strip shaping (tape-casting), scraping blade method (doctor-blading), serigraphy (Screen- Printing), the method such as ink jet printing or thermal imaging (Thermal-Imaging) reduces number of plies manufacture.
The organic electroluminescence device that the present invention provides according to the material using also can be divided into above luminous, back side illuminated or Lighting at two sides；And this organic electroluminescence device can be applied in organic luminescent device (OLED), organic sun with same principle On battery (OSC), Electronic Paper (e-paper), Organophotoreceptor (OPC) or OTFT (OTFT).
The heteroaromatic derivative shown in formula (I) that the present invention provides is in organic photovoltaic cell, illumination OLED, flexibility Also can be suitable for according to the principle being suitable for organic luminescent device in the organic assemblies such as OLED, Organophotoreceptor and organic transistor.
Present invention also offers a kind of organic photoelectrical material, including the isoquinoline compound shown in above-mentioned formula (I)；Described Organic photoelectrical material includes organic photovoltaic cell, Electronic Paper, Organophotoreceptor or organic transistor.
In order to further illustrate the present invention, the heteroaromatic derivative present invention being provided with reference to embodiment and its preparation Method and organic electroluminescence device are described in detail.
Embodiment 1
The synthesis of intermediate 2- chloro- 5- phenyl pyrazines (A-1)：
By bromo- for 2- 5- chloropyrazine (21.3g, 0.11mol), phenyl boric acid (12.2g, 0.10mol), four triphenyl phosphorus palladiums 0.5g, is added in 1000mL reaction bulb, adds toluene 400mL, and aqueous sodium carbonate (2N, 150mL) nitrogen is protected, oil bath 80 DEG C reaction 24 hours.Last handling process：Reaction system is lowered the temperature, 30 minutes points of liquid of standing, retains organic layer, is spin-dried for toluene, solid Add a small amount of dichloromethane dissolving, cross post separation, use petroleum ether：Dichloromethane=1：1 (volume ratio) rushes post, obtains solid (A-1) (10.7g, y=56%).
Embodiment 2
The synthesis of intermediate A -2～A-5：
According to the synthetic method of above-described embodiment 1 intermediate A -1, prepare the change shown in table 1 with same molar ratio Compound, table 1 is that the embodiment of the present invention 2 reactive material, generation material and yield collect.
Table 1 embodiment 2 reactive material, generation material and yield collect
Embodiment 3
The synthesis of the chloro- N of intermediate 5-, N- diphenyl pyrazine -2- amine (A-6)：
By diphenylamines (16.9g, 0.10mol) and sodium tert-butoxide (28g, 0.30mol), toluene 400mL is added to reaction bulb In, stir 30 minutes, nitrogen is protected, and is subsequently adding 2- bromo- 5- chloropyrazine (23.2g, 0.12mol), three (dibenzylideneacetones) Two palladium 1.5g, are eventually adding tri-butyl phosphine 4g, are warmed up to 100 DEG C and react 24 hours.Last handling process：System is lowered the temperature, and adds Water terminating reaction, filters, and filtrate divides liquid, is spin-dried for toluene, adds a small amount of dichloromethane dissolved solid, petroleum ether:Dichloromethane= 3:1 (volume ratio) crosses post separation, obtains solid (A-6) (14.1g, y=50%).
Embodiment 4
According to the synthetic method of above-described embodiment 3 intermediate A -6, prepare chemical combination shown in table 2 with same molar ratio Thing, table 2 is that the embodiment of the present invention 4 reactive material, generation material and yield collect.
Table 2 embodiment of the present invention 4 reactive material, generation material and yield collect
Embodiment 5
The synthesis of intermediate 5- chloro- 2,3- diphenyl pyrazine (A-9)：
By phenyl boric acid (24.4g, 0.20mol), 2,3- bis- bromo- 5- chloroquinolines (27.3g, 0.10mol), tetra-triphenylphosphine palladium (7.0g, 3%) is added in reaction bulb, adds toluene 600mL, and aqueous sodium carbonate (2N, 250mL) nitrogen is protected, oil bath 90 DEG C reaction, overnight.Last handling process：System is lowered the temperature, point liquid, is spin-dried for toluene, residue is entirely molten with dichloromethane, adds equivalent Petroleum ether, cross silica gel funnel, and use dichloromethane：Petroleum ether=1：2 (volume ratio) rinses, and until no product point flows out, receives Collection filtrate, and it is spin-dried for solvent, obtain dark solid (A-9) (21.3g, y=80%).
Embodiment 6
According to the synthetic method of above-described embodiment 5 intermediate A -9, prepare chemical combination shown in table 3 with same molar ratio Thing, table 3 is that the embodiment of the present invention 6 reactive material, generation material and yield collect.
Table 3 embodiment of the present invention 6 reactive material, generation material and yield collect
Embodiment 7
The synthesis of intermediate 5- (4- pyridine radicals) pyrimidine -2-base boric acid (A-13)：
Take 5- (4- pyridine radicals) -2- Bromopyrimidine (10g, 42.4mmol) to be added in there-necked flask, add THF 100mL, nitrogen Gas shielded, -78 DEG C are stirred 30 minutes, are subsequently adding n-BuLi (2.5M) 21mL, react 1 hour, add boric acid three isopropyl Ester 14g, low-temp reaction 1 hour, gradually recovers room temperature.Last handling process, adding 2M hydrochloric acid to make solution pH value in system is 4-5, Standing point liquid, aqueous layer with ethyl acetate extracts one time, merges organic layer, is spin-dried for, obtains white solid (A-13) (6.8g, y= 80%).
Embodiment 8
According to the synthetic method of above-described embodiment 7 intermediate A -13, prepare chemical combination shown in table 4 with same molar ratio Thing, table 4 is that the embodiment of the present invention 8 reactive material, generation material and yield collect.
Table 4 embodiment of the present invention 8 reactive material, generation material and yield collect
Embodiment 9
The synthesis of intermediate 2- (pyridine -2- carbonyl) pyridine carboxylic acid methyl esters (B-1)：
3- bromopyridine (15.9g, 0.1mol) is dissolved in 300mL absolute ether, -78 DEG C of the dry ice bath, nitrogen is protected, adds The BuLi (2.5M) of 44mL, stirring reaction 1 hour, add 3,4- diethyl pyridinedicarboxylate (19.5g, 0.1mol), react 2 Hour, after be gradually raised to room temperature, add water terminating reaction.Last handling process：System divides liquid, branch vibration layer, water layer acetic acid second Ester extracts one time, merges organic layer and is spin-dried for organic solvent, uses dichloromethane:Petroleum ether=9:1 (volume ratio) crosses post separation, obtains White solid (B-1) (12.1g, Y=50%).
Embodiment 10
According to the synthetic method of above-described embodiment 9 intermediate B -1, prepare chemical combination shown in table 5 with same molar ratio Thing, table 5 is that the embodiment of the present invention 10 reactive material, generation material and yield collect.
Table 5 embodiment of the present invention 10 reactive material, generation material and yield collect
Embodiment 11
The synthesis of intermediate pyrido [3,4-g] isoquinolin -5,10- diketone (C-1)：
B-1 (10g, 41.5mmol) prepared by embodiment 9 is dissolved in the THF of 300mL, cools to 0 DEG C, adds mixing Liquid LTMP (the synthesis of LTMP：In the THF of 500mL, 0 DEG C of dissolving 0.13mol BuLi of holding, the 2 of 0.14mol, 2,6,6- tetra- Methyl piperidine).0 DEG C of stirring reaction 2 hours, adds 200mL water terminating reaction, branch vibration layer, organic layer is spin-dried for, and uses dichloromethane Alkane:Petroleum ether=10:1 (volume ratio) crosses post separation, obtains solid (C-1) (3.5g, y=44%).
Embodiment 12
According to the synthetic method of above-described embodiment 11 intermediate C-1, prepare chemical combination shown in table 6 with same molar ratio Thing, table 6 is that the embodiment of the present invention 12 reactive material, generation material and yield collect.
Table 6 embodiment of the present invention 12 reactive material, generation material and yield collect
Embodiment 13
The synthesis of intermediate 5,10- dichloropyridine simultaneously [3,4-g] isoquinolin (D-1)：
The C-1 (10g, 47.8mmol) accurately weighing embodiment 11 preparation is added in reaction bulb, adds 200mL acetonitrile, Weigh 30g POCl3 again to be slowly dropped in reaction bulb, after completion of dropping, be slowly warmed up to 60 DEG C, the reaction time is 5 hours. After completion of the reaction, add the careful extraction of water to go out, then place substantial amounts of saturated solution of sodium carbonate and adjust pH value 7-8, add dichloromethane, Extraction three times, is spin-dried for obtaining solid (D-1) (7.5g, y=63%).
Embodiment 14
According to the synthetic method of above-described embodiment 13 intermediate D-1, prepare chemical combination shown in table 7 with same molar ratio Thing, table 7 is that the embodiment of the present invention 14 reactive material, generation material and yield collect.
Table 7 embodiment of the present invention 14 reactive material, generation material and yield collect
Embodiment 15
The synthesis of 5,10- bis- (4- pyridine radicals) pyrido [3,4-g] isoquinolin (E-1)：
5,10- Dichloro-pendin simultaneously [g] quinoline D-1 (14.8g, 0.6mmol) prepared by embodiment 13,4- pyridine borate (18g, 0.146mmol), tetra-triphenylphosphine palladium 4g is added in reaction bulb, adds toluene, second alcohol and water 2：1：1 (volume ratio) Mixed liquor amounts to 600mL, and nitrogen is protected, and stirring is warmed up to 110 DEG C and reacts 24 hours.Last handling process：System is lowered the temperature, point liquid, It is spin-dried for toluene.Add dichloromethane dissolved solid, cross post, petroleum ether：Ethyl acetate=2：1 (volume ratio) rinses, and obtains solid (E- 1) (13g, y=65%).
Using proton nmr spectra, the compound structure of preparation is characterized, result is as follows：1H NMR(500MHz, Chloroform)δ9.29(s,2H),8.71(s,4H),8.52(s,2H),7.90(s,4H),7.63(s,2H).It can be seen that, this Bright prepare above-claimed cpd E-1.
Embodiment E-2～E-23
According to the synthetic method of above-described embodiment 15 intermediate E -1, prepare chemical combination shown in table 8 with same molar ratio Thing, table 8 is that embodiment of the present invention E-2～E-23 reactive material, generation material and yield collect.
Table 8 embodiment of the present invention E-2～E-23 reactive material, generation material and yield collect
Embodiment F-1～F-9
According to the synthetic method of above-described embodiment 15E-1, with the compound D2～D9 of embodiment 14 preparation as raw material, use phase Prepare compound shown in table 9 with mole ratio, table 9 be embodiment of the present invention F-1～F-9 reactive material, generate material and Yield collects.
Table 9 embodiment of the present invention F-1～F-9 reactive material, generation material and yield collect
Using proton nmr spectra, the compound F-1 structure of preparation is characterized, result is as follows：1H NMR(500MHz, Chloroform) δ 9.54 (s, 1H), 9.29 (s, 1H), 8.71 (s, 4H), 8.52 (s, 1H), 8.33 (s, 2H), 8.12 (s, 1H), 7.90 (s, 4H), 7.63 (s, 1H), 7.52 (d, J=30.0Hz, 3H).It can be seen that, the present invention has prepared above-mentioned chemical combination Thing F-1.
Using proton nmr spectra, the compound F-9 structure of preparation is characterized, result is as follows：1H NMR(500MHz, Chloroform) δ 9.23 (d, J=85.0Hz, 2H), 8.32 (s, 1H), 7.65 (d, J=5.0Hz, 5H), 7.55 (s, 4H), 7.42 (d, J=10.0Hz, 3H), 2.71 (s, 2H), 1.63 (s, 2H), 1.27 (d, J=15.0Hz, 12H), 0.89 (s, 3H). It can be seen that, the present invention has prepared above-claimed cpd F-9.
Embodiment 16
The synthesis of N, N- diphenyl -10- (pyridin-4-yl epoxide) pyrido [3,4-g] isoquinolin -5- amine (G-1)：
1) synthesis of the chloro- N of 10-, N- diphenyl pyrido [3,4-g] isoquinolin -5- amine
According to the synthetic method of embodiment 3 intermediate A -6, with 5,10- dichloropyridine simultaneously [3,4-g] isoquinolin (6.0g, 24mmol), diphenylamines (4.4,24mmol) is reacted for raw material, obtains the chloro- N of intermediate 10-, N- diphenyl pyrido [3,4- G] isoquinolin -5- amine (4.6g, y=50%).
2) synthesis of N, N- diphenyl -10- (pyridin-4-yl epoxide) pyrido [3,4-g] isoquinolin -5- amine (G-1)
Disubstituted-4-hydroxy pyridine (10g, 0.1mol) is dissolved in 100mL anhydrous tetrahydro furan, stirring, precise NaH (0.96g, 0.4mol) is added in reaction bulb in batches, must not be too fast, prevents too many bubble from producing, adds rear solution and assume Huang Color, adds the chloro- N of 10-, N- diphenyl pyrido [3,4-g] isoquinolin -5- amine (42.0g, 0.11mol), also will add in batches Enter, room temperature reaction is overnight.Last handling process：Filter, remove solid matter, filtrate is spin-dried for, add dichloromethane dissolving, cross post and use Petroleum ether：Ethyl acetate=1：5 (volume ratios) rush post, obtain solid (G-1) (22.0g, y=50%).
Using proton nmr spectra, the compound G-1 structure of preparation is characterized, result is as follows：1H NMR(500MHz, Chloroform) δ 9.61 (s, 1H), 9.29 (s, 1H), 8.51 (d, J=15.0Hz, 2H), 8.39 (s, 2H), 7.65 (d, J= 25.0Hz, 2H), 7.24 (s, 4H), 7.14 6.93 (m, 8H).It can be seen that, the present invention has prepared compound shown in above-mentioned G-1.
Embodiment 17
The synthesis of N, N- diphenyl -10- (pyridin-4-yl sulphur) pyrido [3,4-g] isoquinolin -5- amine (G-2)：
By 4- pyridine mercaptan (1.1g, 10mmol), the chloro- N of 10-, N- diphenyl pyrido [3,4-g] isoquinolin -5- amine (3.8g, 10mmol), potassium hydroxide (840mg, 15mmol), mPANI/pFe3O4 (2.5g, 5mol%) H2O (30mL) mixes, Heating 8 hours.Organic phase is extracted by ethyl acetate, and adopts ethyl acetate：Petroleum ether=4:1 (volume ratio) crosses post separation, Obtain white solid (G-2) (1.73g, y=38%).
Using proton nmr spectra, the compound G-2 structure of preparation is characterized, result is as follows：1H NMR(500MHz, Chloroform) δ 9.29 (s, 2H), 8.88 (s, 2H), 8.52 (s, 2H), 7.73 (s, 1H), 7.63 (s, 1H), 7.43 (s, 2H), 7.24 (s, 4H), 7.04 (d, J=40.0Hz, 6H).It can be seen that, the present invention has prepared compound shown in above-mentioned G-2.
Embodiment 18
The synthesis of 5,10- bis- (pyridin-4-yl epoxide) pyrido [3,4-g] isoquinolin (G-3)：
According to the synthetic method of G-1 in embodiment 16, put into D-1 (5.0g, 20mmol), 4- pyridone (4.0g, 42mmol), obtain solid (G-3) (3.4g, y=46%).
Using proton nmr spectra, the compound G-3 structure of preparation is characterized, result is as follows：1H NMR(500MHz, Chloroform) δ 9.42 (s, 2H), 8.50 (s, 2H), 8.39 (s, 4H), 7.76 (s, 2H), 6.98 (s, 4H).It can be seen that, this Bright prepare compound shown in above-mentioned G-3.
Embodiment 19
The synthesis of 5,10- bis- (pyridin-4-yl sulphur) pyrido [3,4-g] isoquinolin (G-4)：
According to the synthetic method of G-2 in embodiment 17, add 4- pyridine mercaptan (2.2g, 20m mol), 5,10- dichloro pyrroles Pyridine [3,4-g] isoquinolin (2.5g, 10mmol) obtains white solid (G-4) (1.4g, y=35%).
Using proton nmr spectra, the compound G-4 structure of preparation is characterized, result is as follows：1H NMR(500MHz, Chloroform) δ 9.29 (s, 1H), 8.88 (s, 2H), 8.52 (s, 1H), 7.63 (s, 1H), 7.43 (s, 2H).It can be seen that, this Bright prepare compound shown in above-mentioned G-4.
Embodiment 20
Fisher Co., Ltd's coating layer thickness isIto glass substrate be placed in distilled water clean 2 times, ultrasonic wave is washed Wash 30min, then wash 30min in order by isopropanol, acetone, methyl alcohol, more repeatedly cleaned 2 times with distilled water, ultrasonic wave is washed Wash 10min, be dried, transfer in plasma washing machine, aforesaid substrate is washed 5min, deliver in evaporator；Will be accurate Evaporation hole injection layer 2-TNATA evaporation on the ito transparent electrode got readyHole transmission layer a-NPD is deposited withBlue or green The TPPDA evaporation of color main body A DN/ doping 5%Hole blocking layer and hole transmission layer are deposited with as shown in table 10Cloudy Pole LiFAlObtain organic electroluminescence device；Said process organic matter vaporization plating speed is to maintainLiF isAl is
The electron luminescence characteristic of the organic luminescent device that said method obtains is shown in Table 10.
The electronics of hole blocking layer and hole transmission layer substance classes and organic electroluminescence device in table 10 embodiment 20 The characteristics of luminescence
It can be seen that utilizing the organic electroluminescence device of heteroaromatic derivative preparation of the present invention from above-mentioned table 10 Luminous efficiency and life characteristic all increase significantly.
The present invention prepares organic electroluminescence device using new heteroaromatic derivative, has higher luminous efficiency Longer lifetime results, therefore can be applicable to the high OLED industry of practicality.The organic electroluminescence device of the present invention can be fitted Show for flat panel, planar illuminant, illumination face illuminating OLED illuminator, flexible illuminator, duplicator, printer, The light source of LCD backlight lamp or dosing machine class, display board, mark etc..
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that it is right For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out Some improvement and modification, these improve and modify and also fall in the protection domain of the claims in the present invention.

Claims (10)

1. a kind of heteroaromatic derivative, has structure shown in formula (I)：
Wherein,
L1、L2、L3、L4Independent selected from 0 or 1；
Q1And Q2The independent aryl selected from carbon number 6～30 or the heterocyclic radical of carbon number 1～30；
R1Selected from hydrogen atom, cyano group, carbon number be 1～30 alkyl, the aryl of substituted or unsubstituted carbon number 6～50, The heterocyclic radical of substituted or unsubstituted carbon number 5～50, the aromatic series amido of substituted or unsubstituted carbon number 7～30, The aralkoxy of substituted or unsubstituted carbon number 7～30 or the aralkyl sulfydryl of substituted or unsubstituted carbon number 7～30；
Ar1、Ar2、Ar3、Ar4Independent selected from hydrogen atom, the aralkyl of substituted or unsubstituted carbon number 7～50, replacement or The aralkoxy of unsubstituted carbon number 7～50, the aralkyl sulfydryl of substituted or unsubstituted carbon number 7～50, carbon atom The aryl of number 6～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, substituted or unsubstituted carbon number 7～30 Aromatic series amido.
2. heteroaromatic derivative according to claim 1 is it is characterised in that described heteroaromatic derivative has following knot Structure：
Wherein,
Z1～Z16Independent selected from CH, C or N；
L3And L4Independent selected from 0 or 1；
R1Selected from hydrogen atom, cyano group, carbon number be 1～30 alkyl, the aryl of substituted or unsubstituted carbon number 6～50, The heterocyclic radical of substituted or unsubstituted carbon number 5～50, the aromatic series amido of substituted or unsubstituted carbon number 7～30, The aralkoxy of substituted or unsubstituted carbon number 7～30 or the aralkyl sulfydryl of substituted or unsubstituted carbon number 7～30；
Ar1、Ar2、Ar3、Ar4Independent selected from hydrogen atom, the aralkyl of substituted or unsubstituted carbon number 7～50, replacement or The aralkoxy of unsubstituted carbon number 7～50, the aralkyl sulfydryl of substituted or unsubstituted carbon number 7～50, carbon atom The aryl of number 6～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, substituted or unsubstituted carbon number 7～30 Aromatic series amido.
3. heteroaromatic derivative according to claim 1 is it is characterised in that in described heteroaromatic derivative ,-R1Selected from Lower structure：
Wherein,
Z1～Z8Independent selected from CH, C or N；
R'1And R'2Independent selected from carbon number be 1～30 alkyl, aryl of carbon number 6～50, substituted or unsubstituted The aromatic series amido of the heterocyclic radical of carbon number 5～50 or substituted or unsubstituted carbon number 6～30.
4. the heteroaromatic derivative according to claims 1 to 3 any one is it is characterised in that described heteroaromatic derivative In ,-Ar1、-Ar2、-Ar3、-Ar4Independent selected from following formula (1)～structure shown in formula (35)：
Wherein,
X and Y independence selected from hydrogen atom, halogen atom, cyano group, the alkyl of substituted or unsubstituted carbon number 1～30, replacement Or the alkoxyl of unsubstituted carbon number 1～30, the thiazolinyl of substituted or unsubstituted carbon number 2～30, replacement or do not take The aralkyl of carbon number 7～30 in generation, the aralkoxy of substituted or unsubstituted carbon number 7～30, replacement or unsubstituted The aryl of carbon number 6～30, the aryloxy group of substituted or unsubstituted carbon number 6～30, substituted or unsubstituted carbon former The aromatic series amido of the heterocyclic radical of subnumber 5～30 or substituted or unsubstituted carbon number 7～30.
5. heteroaromatic derivative according to claim 1 is it is characterised in that work as Q1And Q2It is all phenyl, R1For cyano group or benzene During base, Ar1And Ar2The independent aryl selected from substituted or unsubstituted carbon number 7～50, substituted or unsubstituted carbon atom The aromatic series amido of the heterocyclic radical of number 5～50 or substituted or unsubstituted carbon number 7～30.
6. heteroaromatic derivative according to claim 1 is it is characterised in that L1And L2It is asynchronously 0.
7. a kind of preparation method of heteroaromatic derivative, including：
Compound shown in formula (III) is reacted with the compound shown in the compound shown in formula (IV) and formula (V), is obtained Heteroaromatic derivative shown in formula (I)；
Wherein,
X ' is halogen atom, Y ' and Y1' independent selected from B (OH)2Or H；
L1、L2、L3、L4Independent selected from 0 or 1；
Q1And Q2The independent aryl selected from carbon number 6～30 or the heterocyclic radical of carbon number 1～30；
R1Selected from hydrogen atom, cyano group, carbon number be 1～30 alkyl, the aryl of substituted or unsubstituted carbon number 6～50, The heterocyclic radical of substituted or unsubstituted carbon number 5～50, the aromatic series amido of substituted or unsubstituted carbon number 7～30, The aralkoxy of substituted or unsubstituted carbon number 7～30 or the aralkyl sulfydryl of substituted or unsubstituted carbon number 7～30；
Ar1、Ar2、Ar3、Ar4Independent selected from hydrogen atom, the aralkyl of substituted or unsubstituted carbon number 7～50, replacement or The aralkoxy of unsubstituted carbon number 7～50, the aralkyl sulfydryl of substituted or unsubstituted carbon number 7～50, carbon atom The aryl of number 6～50, the heterocyclic radical of substituted or unsubstituted carbon number 5～50, substituted or unsubstituted carbon number 7～30 Aromatic series amido.
8. a kind of organic electroluminescence device, will including the heteroaromatic derivative described in claim 1～6 any one or right Seek heteroaromatic derivative prepared by the preparation method described in 7.
9. organic electroluminescence device according to claim 8 it is characterised in that include first electrode, second electrode and It is arranged at the organic matter layer between described first electrode and second electrode；It is any one that described organic matter layer includes claim 1～6 Heteroaromatic derivative described in or the heteroaromatic derivative of the preparation of the preparation method described in claim 7.
10. a kind of organic photoelectrical material is it is characterised in that include the heteroaromatic compounds described in claim 1～6 any one Or the heteroaromatic compounds of the preparation method preparation described in claim 7；Described organic photoelectrical material include organic photovoltaic cell, Electronic Paper, Organophotoreceptor or organic transistor.
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EP0394846A2 (en) * 1989-04-27 1990-10-31 Sekisui Kagaku Kogyo Kabushiki Kaisha Organic photochromic compound
CN101684095A (en) * 2008-06-24 2010-03-31 葛来西雅帝史派有限公司 Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN102675031A (en) * 2012-05-22 2012-09-19 吉林奥来德光电材料股份有限公司 Beta-dinaphthyl anthracene and derivative thereof and preparation method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0394846A2 (en) * 1989-04-27 1990-10-31 Sekisui Kagaku Kogyo Kabushiki Kaisha Organic photochromic compound
CN101684095A (en) * 2008-06-24 2010-03-31 葛来西雅帝史派有限公司 Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN102675031A (en) * 2012-05-22 2012-09-19 吉林奥来德光电材料股份有限公司 Beta-dinaphthyl anthracene and derivative thereof and preparation method

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