CN106588531A - Spiro ring organic photoelectric material, preparation method and applications thereof - Google Patents

Spiro ring organic photoelectric material, preparation method and applications thereof Download PDF

Info

Publication number
CN106588531A
CN106588531A CN201610867745.7A CN201610867745A CN106588531A CN 106588531 A CN106588531 A CN 106588531A CN 201610867745 A CN201610867745 A CN 201610867745A CN 106588531 A CN106588531 A CN 106588531A
Authority
CN
China
Prior art keywords
raw material
under
reaction
organic
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610867745.7A
Other languages
Chinese (zh)
Other versions
CN106588531B (en
Inventor
张善国
葛立权
耿崴
林存生
付文岗
胡葆华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Valiant Co Ltd
Original Assignee
Valiant Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Valiant Co Ltd filed Critical Valiant Co Ltd
Priority to CN201610867745.7A priority Critical patent/CN106588531B/en
Publication of CN106588531A publication Critical patent/CN106588531A/en
Application granted granted Critical
Publication of CN106588531B publication Critical patent/CN106588531B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/72—Spiro hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/52—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of six-membered aromatic rings being part of condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/127—Preparation from compounds containing pyridine rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Abstract

The present invention relates to a spiro ring organic photoelectric material and a preparation method thereof, and an organic electroluminescent device containing the spiro ring organic photoelectric material. According to the present invention, the provided organic electroluminescent device contains the spiro ring organic photoelectric material, such that the quantum efficiency, the current efficiency, the power efficiency and the brightness of the organic electroluminescent device can be substantially improved while the driving voltage is substantially reduced so as to significantly improve the service life of the organic electroluminescent device.

Description

A kind of volution organic photoelectrical material and its preparation method and application
Technical field
The present invention relates to field of photoelectric technology, more particularly to a kind of volution organic photoelectrical material, its preparation method and its should With.
Background technology
The origin of organic electroluminescence device (organic light emitting diode, referred to as OLED) can be chased after Trace back to nineteen sixties, Pope et al. makes it light with anthracene single crystal impressed DC voltage, but because driving voltage it is high (100V) and luminosity and efficiency are all than relatively low, too many attention is not caused.With updating for technology. C.W.Tang of Kodak Company in 1987 et al. with 8-hydroxyquinoline aluminium (Alq3) as luminescent material, using the side of vacuum evaporation Method has made the OLED with double layer sandwich structure, opens bright voltage and only has several volts, and brightness reaches as high as 1000cd/m2, thus, Mark OLED has stepped an important step towards practical, so as to become an important milestone of field of organic electroluminescence.
At present, include for OLED proposes high performance research：The driving voltage of device is reduced, the luminous efficiency of device is improved And improve the service life of device etc..In order to realize the continuous lifting of the performance of OLED, not only need from the structure of OLED with And the innovation of the manufacture craft of OLED, constantly studied and innovated with greater need for the photoelectric material used in OLED, create Make the photoelectric functional material applied in OLED of higher performance.
The photoelectric functional material being previously mentioned can be divided into two big class, i.e. electric charge injection transmission material and luminous material from purposes Material, further, can also inject charge into transmission material and be divided into electron injection transmission material, electron-blocking materials, hole injection Transmission material and hole barrier materials, can also be divided into main body luminescent material and dopant material by luminescent material.
In order to make high performance OLED, it is desirable to which photoelectric functional material possesses good photoelectric characteristic, for example, as electric charge Transmission material, it is desirable to which it has good carrier mobility and higher glass transition temperature etc., and as luminescent layer Material of main part requires that material has a good bipolarity, and appropriate highest occupied molecular orbital (abbreviation HOMO)/minimum is not accounted for Molecular orbit (abbreviation LUMO) energy rank etc..
OLED at least include two-layer above structure, it should be pointed out that the OLED applied in industry include hole injection layer, The several functions film such as hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and electron injecting layer Layer, that is to say, that the photoelectric functional material for being applied to OLED includes hole-injecting material, hole mobile material, luminescent material, electricity Sub- injection material etc., it can be seen that it is rich and multifarious to apply material type and collocation form in OLED to have Feature.In addition, for the OLED of different structure, the photoelectric functional material for being used has stronger selectivity, identical Performance of the material in the OLED of different structure, it is also possible to completely totally different.
Therefore, for the industry application requirement of current OLED, and the difference in functionality film layer and photoelectric characteristic demand of OLED, Must select to be more suitable for, with high performance photoelectric functional material or combination of materials, high efficiency, the length of OLED could be realized Life-span and the overall characteristic of low-voltage.For the actual demand that current OLED shows Lighting Industry, apply at present in OLED Photoelectric functional material development it is also far from enough, lag behind the requirement of panel manufacturing enterprise, it is higher as material enterprise development The exploitation of the organic functional material of performance is particularly important.
The content of the invention
In order to solve the above problems, the applicant is studied with keen determination, is as a result found：Organic light provided by the present invention Electric material, with high heat endurance and high glass transition temperature, as the luminescent layer material of main part of OLED so that OLED Current efficiency is obtained, power efficiency and quantum efficiency are greatly improved, while also greatly promoting the life-span of OLED.
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations For clear, clear and definite.
It is an object of the invention to provide a kind of volution organic photoelectrical material, its formula is by shown in following formula I or Formula II：
In above-mentioned formula I, Formula II, A is a kind of in phenylene or naphthylene, and its structural formula is as follows：
Wherein, * is represented and the binding site for being capable of cyclization.
Below formula is can be described as so as to organic photoelectrical material of the present invention：
In I～formula of formula Ⅹ, R1、R2It is each independently selected from hydrogen-based (- H), halogen, cyano group (- CN), nitro (- NO2), it is different Thiocyanogen (- N=S=O), sulfonyl, sulfoxide group, amide groups, carbon number are 1～10 alkyl and replace or unsubstituted Carbon number be one kind in 1～12 alkoxyl, wherein, R1And R2Can be identical group, alternatively different groups.
As the example of halogen, specifically can enumerate：Fluorine-based (- F), chloro (- Cl), bromo (- Br), preferably fluorine-based (- F)。
Sulfonyl is represented by：-SO2R, amide groups is represented by：- CO-NHR or-CO-NRR, sulfoxide group is represented by：- SOR, wherein, in above-mentioned mentioned sulfonyl, amide groups and sulfoxide group, R may be selected from the one kind in following radicals：First Base, trifluoromethyl, phenyl, pentafluorophenyl group, 4- aminomethyl phenyls, 4- tert-butyl-phenyls, 4- isopropyl phenyls and 4- cyano-phenyls.
Carbon number is 1～10 alkyl, and alkyl can be chain-like alkyl, alternatively cycloalkyl, on the ring of cycloalkyl Hydrogen can be replaced by alkyl, in the alkyl the preferred lower limit of carbon number be 2,3,4,5, preferred higher limit be 3,4,5, 6,8.As the example of alkyl, specifically can enumerate：Methyl (- CH3), ethyl (- C2H5), n-propyl, isopropyl (- CH (CH3)2), normal-butyl, isobutyl group, sec-butyl, the tert-butyl group (- C (CH3)3), n-pentyl, isopentyl, neopentyl, cyclopenta, hexamethylene Base
When it is 1～12 alkoxyl to choose carbon number, it is preferable that the alkoxyl for selecting carbon number to be 1～10, enter One step preferably, selects the alkoxyl that carbon number is 1～6, it is further preferred that selecting the alcoxyl that carbon number is 1～4 Base.As the example of alkoxyl, specifically can enumerate：It is methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, secondary Butoxy, tert-butoxy, n-pentyloxy, isoamoxy, cyclopentyloxy, cyclohexyloxy.In addition, when carbon number is 1～12 Alkoxyl can replace to form halogenated alkoxy by one or more in halogen atom such as F, Cl and Br.
In above-mentioned I～formula of formula Ⅹ, Ar1、Ar2Be each independently selected from hydrogen-based, deuterium base, fluorine-based, chloro, cyano group, phenyl, Carbon number be 7～14 benzene alkyl, the conjugated polycyclic aryl that carbon number is 10～60 and containing in N, S, O at least A kind of carbon number is the one kind in 12～60 aromatic heterocyclic radicals, wherein Ar1And Ar2Can be identical group, it is alternatively different Group.
In the benzene alkyl that carbon number is 7～14, the preferred lower limit of carbon number is 8,9,10, preferably higher limit For 9,10,11,12,13,14, as the example of benzene alkyl, specifically can enumerate：4- aminomethyl phenyls, 4- isopropyls, the 4- tert-butyl groups Phenyl, 4- cyclohexyl phenyls.When choosing is with above-mentioned conjugated polycyclic aryl, preferred carbon number is 10～32 conjugated polycyclic virtue Base.
In aromatic heterocyclic radical, carbon number is preferably 12～30.
As Ar1And Ar2Example, specifically can enumerate：
Wherein, * represents the binding site that can be bonded with mother nucleus structure.
It should be noted that Ar1With Ar2The representative substituted radical for its representative compound, for example, work as Ar1And Ar2 When being benzene, then Ar1And Ar2It is phenyl, and Ar1And Ar2When being biphenyl, then Ar1And Ar2It is xenyl.
As the example of organic photoelectrical material, specifically can enumerate：
By test result indicate that, the organic photoelectrical material that the present invention is provided has high heat endurance and high vitrifying Transition temperature, applies in OLED as the luminescent layer material of main part of OLED, the organic photoelectrical material provided comprising the present invention OLED can obtain good device and show, the current efficiency of such as OLED, and power efficiency and quantum efficiency obtain changing greatly very much It is kind；Simultaneously, additionally it is possible to greatly promote the life-span of OLED.In addition, the space structure of the organic photoelectrical material of present invention offer is torsion Bent nonplanar structure, can be prevented effectively from the tight accumulation of molecule.It is possible thereby to learn：The organic photoelectrical material that the present invention is provided There is good application effect in OLED, with good industrialization prospect.
The present invention is also claimed the preparation method of organic photoelectrical material, comprises the following steps：
1) with raw material 1 and trifluoromethanesulfanhydride anhydride as raw material, the reaction under the conditions of inert atmosphere neutral and alkali generates intermediate 1；
2) step 1) in the basic conditions reaction generates intermediate under catalyst action for the intermediate 1 and the aryl boric acid that obtain 2；
3) with raw material 2 and duplex pinacol borate as raw material, in reaction acquisition under catalyst action under alkalescence condition Mesosome 3, catalyst is selected from Pd (dppf) Cl2、Pd(PPh3)2Cl2In one kind；
4) by step 2) in the intermediate 2 and the step 3 that obtain) in gained intermediate 3 in inert atmosphere neutral and alkali condition Lower lower reaction of catalyst effect generates intermediate 4；
5) by step 4) in gained intermediate 4 there is ester hydrolysis reaction under inert gas shielding under alkalescence condition, obtain Must be containing the reaction system of intermediate 5；
6) by step 5) in obtain intermediate 5 react in acidic organic solvent under inert gas shielding generate intermediate 6；
7) occur after substitution reaction, to the reactant under inert gas shielding as raw material with raw material 3 and organolithium reagent In system add step 6) in obtain intermediate 6 organic solution, obtain the reaction system containing intermediate 7；
8) by step 7) in intermediate 7 and the raw material 4 of gained acquisition is reacted in aromatic hydrocarbon solvent under inert gas shielding Reaction system containing intermediate 8, the raw material 4 is one or more in P-TOLUENE SULFO ACID 99, methanesulfonic acid and trifluoroacetic acid；
9) by step 8) in the intermediate 8 and the aryl bromo-derivative Ar that obtain2- Br under inert gas shielding, catalyst with Volution organic photoelectrical material is obtained under alkalescence condition effect in reaction；Wherein, step 2), 4), 9) described in catalyst be selected from Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2And Pd2(dba)3In one or more；
Synthetic route is as follows：
Further, the preparation method of the volution organic photoelectrical material comprises the steps：
(1) under the protection of inert gas and under -20～30 DEG C of temperature conditionss, trifluoromethanesulfanhydride anhydride is added to Reacted in organic solution containing raw material 1 and triethylamine, the reaction system containing intermediate 1 is obtained, in above-mentioned formula 1 and formula In 2, group A is in the organic photoelectrical material of aforementioned offer it was mentioned that the invention that so repeating no more.
In the step (1), by raw material 1 and triethylamine Monodispersed in dichloroethanes, the addition of trifluoromethanesulfanhydride anhydride It is trifluoromethanesulfanhydride anhydride with the mol ratio of raw material 1 that amount causes trifluoromethanesulfanhydride anhydride：Raw material 1=1～1.2：1, triethylamine with it is former The mol ratio of material 1 is triethylamine：Raw material 1=1～1.5:1.
(2) intermediate 1, the aryl boric acid Ar that will be obtained in step (1)1-B(OH)2, alkaline substance solution and catalyst In adding organic solvent, react 2～24 hours under the protection of inert gas and at 0～90 DEG C, obtain and contain intermediate 2 Reaction system, wherein one kind in tetrahydrofuran, toluene, dioxane and the dimethyl acetamide of organic solvent or Various, the alkaline matter is selected from one or more in potassium carbonate, sodium carbonate and potassium phosphate, and the catalyst is selected from Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2And Pd2(dba)3In one or more；
In the step (2), the aryl boric acid Ar1-B(OH)2Addition for cause aryl boric acid Ar1-B(OH)2 It is aryl boric acid Ar with the mol ratio of the intermediate 11-B(OH)2：Intermediate 1=0.5～1.0:1, the alkaline matter is with The mol ratio of mesosome 1 is alkaline matter：Intermediate 2=1～2:1, the addition of the catalyst is for so that catalyst and centre The mol ratio of body 1 is 0.001～0.1:1.
(3) will be in raw material 2, duplex pinacol borate (CAS-RN：73183-34-3), catalyst and alkaline matter are added To in toluene, dimethylbenzene, trimethylbenzene, DMF or dimethyl acetamide, under the protection of inert gas and At 0～150 DEG C, in reaction 2～24 hours, the reaction system containing intermediate 3 is obtained, wherein, catalyst is selected from Pd (dppf)Cl2With Pd (PPh3)2Cl2One kind, the one kind or many of alkaline matter in potassium acetate, potassium phosphate and the potassium carbonate Kind；
In the step (3), the addition of duplex pinacol borate causes duplex pinacol borate with raw material 2 The ratio of mole is duplex pinacol borate：Raw material 2=1～2：1；The alkaline matter is alkalescence with the mol ratio of raw material 2 Material：Raw material 2=1～2:1, the addition of the catalyst is to cause catalyst to be 0.001～0.1 with the mol ratio of raw material 2: 1。
(4) intermediate 2, alkaline substance solution that obtains in the intermediate 3, step (2) that will be obtained in step (3) and urge Agent is added in organic solvent, is reacted 2～24 hours under the protection of inert gas and at 0～90 DEG C, in being contained The reaction system of mesosome 4, wherein organic solvent are selected from tetrahydrofuran, toluene, dioxane and dimethyl acetamide Plant or various, the alkaline matter is selected from one or more in potassium carbonate, sodium carbonate and potassium phosphate, the catalyst is selected from Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2And Pd2(dba)3In one or more；
In the step (4), the addition of the intermediate 3 is the mol ratio for causing intermediate 3 and the intermediate 2 For intermediate 3：Intermediate 2=1.0～2.0:1, the alkaline matter is alkaline matter with the mol ratio of intermediate 2：Intermediate 2 =1～2:1, the addition of the catalyst is to cause catalyst to be 0.001～0.1 with the mol ratio of intermediate 2:1.
(5) intermediate 4 obtained in step (4) and alkaline matter are added in organic solvent, in the protection of inert gas React 2～24 hours down and at 0～130 DEG C, obtain the reaction system containing intermediate 5, wherein organic solvent is selected from just One or more in butanol, sec-butyl alcohol, ethanol and normal propyl alcohol, the alkaline matter is selected from NaOH and potassium hydroxide In one kind, wherein, as shown in following formula 7, wherein X represents hydrogen-based, deuterium base, fluorine-based, chloro or cyano group to intermediate 5；
In the step (5), the addition of the alkaline matter be cause the alkaline matter and intermediate 4 mole Than for alkaline matter：Intermediate 4=1～4:1.
(6) intermediate 5 obtained in step (5) is added in organic solvent, under the protection of inert gas and 0～ React 2～24 hours at 150 DEG C, obtain the reaction system containing intermediate 6, wherein organic solvent is selected from methanesulfonic acid and fluoroform One kind in sulfonic acid, wherein, as shown in following formula 8, wherein X represents hydrogen-based, deuterium base, fluorine-based, chloro or cyano group to intermediate 6；
In the step (6), the addition of the organic solvent be cause the organic solvent and intermediate 5 mole Than for organic solvent：Intermediate 5=10～30:1.
(7) under the protection of inert gas and under -100～0 DEG C of temperature conditionss, by n-BuLi be added to containing Reacted in the organic solution of raw material 3, backward reaction system in add the organic molten of the intermediate 6 that obtains in step (6) Liquid, obtains the reaction system containing intermediate 7, and wherein organic solvent is selected from THF；
In the step (7), it is described by raw material 3 and the Monodispersed of intermediate 6 in tetrahydrofuran, the addition of n-BuLi It is n-BuLi with the mol ratio of raw material 3 that amount causes n-BuLi：Raw material 3=1～1.2：1, raw material 3 rubs with intermediate 6 You are than being raw material 3：Intermediate 6=1～1.2:1.
(8) intermediate 7 and raw material 4 that obtain in step (7) are added in aromatic hydrocarbon solvent, in the guarantor of inert gas Under shield and at 0～150 DEG C, react 2～24 hours, obtain the reaction system containing intermediate 8, wherein, aromatic hydrocarbon solvent One or more in toluene, dimethylbenzene and trimethylbenzene, raw material 4 is selected from P-TOLUENE SULFO ACID 99, methanesulfonic acid and trifluoroacetic acid In one or more,
In the step (8), it is raw material 4 with the ratio of the mole of intermediate 7 that the addition of raw material 4 causes raw material 4：In Mesosome 7=1～2：1.
(9) intermediate 8, the aryl bromo-derivative Ar that will be obtained in step (8)2- Br, alkaline substance solution and catalyst In adding organic solvent, react 2～24 hours under the protection of inert gas and at 0～90 DEG C, obtain containing the present invention The reaction system of organic photoelectrical material, wherein organic solvent are selected from tetrahydrofuran, toluene, dioxane and dimethylacetamide One or more in amine, the alkaline matter is selected from one or more in potassium carbonate, sodium carbonate and potassium phosphate, the catalysis Agent is selected from Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2And Pd2(dba)3In one or more.
In the step (9), the aryl bromo-derivative Ar2The addition of-Br is for so that aryl bromo-derivative Ar2- Br and institute The mol ratio for stating intermediate 8 is aryl bromo-derivative Ar2-Br：Intermediate 8=1.0～2.0:1, the alkaline matter and intermediate 8 Mol ratio be alkaline matter：Intermediate 8=1～2:1, the addition of the catalyst is to cause catalyst and intermediate 8 Mol ratio is 0.001～0.1:1.
In above-mentioned preparation method, the inert gas is selected from one or more in nitrogen, argon gas and helium, preferably Nitrogen.
The preparation method of the organic photoelectrical material that the present invention is provided is simple and easy, it is easy to operate, and with low cost, is conducive to It is large-scale to promote.
The present invention is also claimed a kind of organic electroluminescence device, is provided between the anode and negative electrode of the luminescent device At least one luminescent layer, the luminescent layer is made up of organic photoelectrical material of the present invention.The organic photoelectric that the present invention is provided Material as material of main part with can jointly prepare luminescent layer as the material of dopant material.When in organic electroluminescence device When comprising only luminescent layer, luminescent layer is sandwiched between the anode and cathode, wherein, anode is arranged on transparent substrate layer.
In above-mentioned organic electroluminescence device, as shown in figure 1, may also include one or more in following film layer：It is empty Cave implanted layer 3, hole transmission layer 4, electron transfer layer 6 and electron injecting layer 7, wherein, hole injection layer 3 and hole transmission layer 4 Be arranged between anode 2 and luminescent layer 5, electron transfer layer 6 and electron injecting layer 7 be arranged at luminescent layer 5 and negative electrode 8 it Between.When containing one or more in film layer mentioned above, the structure of organic electroluminescence device can be as follows, but not It is confined to following several：
(1) negative electrode 8 of 2/ organic luminous layer of anode, 5/ electron transfer layer 7/, that is to say, that set between anode 2 and negative electrode 8 Organic luminous layer 5 and electron transfer layer 7 are equipped with, wherein, organic luminescent layer 5 and electron transfer layer 7 are set gradually on anode 2.
(2) negative electrode 8 of 2/ hole injection layer of anode, 3/ organic luminous layer, 5/ electron transfer layer 7/, that is to say, that in the He of anode 2 Hole injection layer 3, organic luminous layer 5 and electron transfer layer 7 are provided between negative electrode 8, wherein, set gradually sky on anode 2 Cave implanted layer 3, organic luminous layer 5 and electron transfer layer 7.
(3) negative electrode 8 of 2/ hole transmission layer of anode, 4/ organic luminous layer, 5/ electron transfer layer 7/, that is to say, that in the He of anode 2 Hole transmission layer 4, organic luminous layer 5 and electron transfer layer 7 are provided between negative electrode 8, wherein, set gradually sky on anode 2 Cave transport layer 4, organic luminous layer 5 and electron transfer layer 7.
(4) negative electrode 8 of 2/ hole injection layer of anode, 3/ hole transmission layer, 4/ organic luminous layer, 5/ electron transfer layer 6/, that is, Say, hole injection layer 3, hole transmission layer 4, organic luminous layer 5 and electron transfer layer 6 be provided between anode 2 and negative electrode 8, Wherein, hole injection layer 3, hole transmission layer 4, organic luminous layer 5 and electron transfer layer 6 are set gradually on anode 2.
The organic electroluminescence that the present invention is provided is prepared from conventional method, has no special demand.
Beneficial effect of the present invention：
The invention provides a class spiral shell type electroluminescent organic material, and there is provided the synthetic method of such material, with this Material illustrates preferable efficiency as the OLED of luminescent materials, and its feature is：
1., by certain chemical method, the electroluminescent organic material that a class has spiral shell type structure is prepared for.
2. such material has preferable thin film stability and suitable molecular entergy level, can as blue emitting material, Apply in field of organic electroluminescence.
3. such material has good heat endurance, and glass transition temperature and decomposition temperature are all very high, is easily formed Good amorphous thin film, applies in electroluminescent device, it is possible to obtain more stable effect and longer service life.
4. in the organic electroluminescence that the present invention is provided, due to the organic photoelectrical material provided containing the present invention, energy The power efficiency of organic electroluminescence is enough greatly improved, at the same time, driving voltage is also reduced, has thus been significantly improved The life-span of organic electro luminescent device.
Description of the drawings
The structural representation of the organic electroluminescence that Fig. 1 is provided for the present invention.
Drawing reference numeral explanation：
1- transparent substrate layers, 2- anodes, 3- hole injection layers, 4- hole transmission layers, 5- luminescent layers, 6- electron transfer layers, 7- electron injecting layers, 8- negative electrodes.
Specific embodiment
The application is further described below by way of instantiation.But these examples are only exemplary, not to this The protection domain of application constitutes any restriction.
In following embodiments, comparative example, reagent, material and the instrument for using as without special explanation, It is commercially available for conventional reagent, conventional material and conventional instrument, wherein involved reagent also can be by being conventionally synthesized Method synthesis is obtained.
Embodiment one, prepare organic photoelectrical material
Embodiment 1The compound 1 that preparation is previously mentioned
(1) preparation of compound 1-a：
At -15 DEG C and under the protection of nitrogen, the bromo- 4-HBA methyl esters (100.0mmol) of 23.1g 2- are taken It is dispersed in 200g dichloroethanes with 121.4g (120mmol) triethylamine, 31.0 trifluoromethanesulfanhydride anhydrides is then added dropwise (110mmol), after completion of dropping, then reaction system is to slowly warm up to room temperature by insulation reaction 2.0 hours, then by above-mentioned body System pour in 200g water, stirring reaction 30min, system layering is washed from water, most at last organic phase decompression desolventizing To without cut, 36.1g compound 1-a are acquired, without the need for being further purified.
(2) preparation of compound 1-b：
Take 36.1g compound 1-a (100.0mmol), 20.7g potassium carbonate (150mmol), the 80g obtained in step (1) Water, 11.0g phenyl boric acids (90mmol) and 260g toluene, under the protection of nitrogen, add catalyst 0.9g Pd (PPh3)4 (0.75mmol), backflow is then heated to, while tracking reaction process using thin-layered chromatography (TLC), has been reacted within about 7.0 hours Bi Hou, after being down to room temperature, system layering after then washing with water, by organic phase decompression desolventizing to without cut, then uses oil Ether acetic acid ethyl ester mixed liquor carries out column chromatography purifying to residue, and wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Second Acetoacetic ester=20:1,13.7g compound 1-b are obtained, yield is 52.29%.
(3) preparation of compound 1-c：
Take the bromo- 5- chlorine acenaphthylenes (100.0mmol) of raw material 26.5g 1-, the duplex of 14.7g potassium acetates (150mmol) 30.5 frequency that Alcohol borate (120mmol) is added in 250g toluene, under the protection of nitrogen, adds catalyst 0.8g Pd (dppf) Cl2 (1mmol), backflow is then heated to, fraction water device water-dividing is selected in course of reaction, while anti-using thin-layered chromatography (TLC) tracking Process is answered, about 5.0 hours after completion of the reaction, add 200g water, system layering, after then washing with water, by the anhydrous sulphur of organic phase Sour sodium is dried, and then toluene carries out column chromatography purifying, obtains 25.9g compound 1-c, and yield is 83.01%.
(4) preparation of compound 1-d：
Take the compound 1-b (13.1g, 45.0mmol) obtained in step (2), the compound 1-c for taking acquisition in step (3) (15.6g, 50.0mmol), 12.4g potassium carbonate (90mmol), 50g water and 140g toluene, under the protection of nitrogen, add catalysis Agent 0.5g Pd (PPh3)4(0.45mmol), backflow is then heated to, while reaction process is tracked using thin-layered chromatography (TLC), About 6.0 hours after completion of the reaction, and after being down to room temperature, organic phase after then washing with water, is reduced pressure desolventizing to nothing by system layering Cut, then obtains 14.4g compound 1-d with toluene ethyl alcohol recrystallization, and yield is 80.89%.
(5) preparation of compound 1-e：
By the compound 1-d (11.9g, 30.0mmol) obtained in step (4), NaOH (2.5g, 60mmol, 96%) And n-butanol 100g, under nitrogen protection, react 4.0 hours at 100～105 DEG C, while TLC tracking reaction process.Instead After should finishing, 200g water quenchings are added to go out reaction, twice, most at last organic phase reduces pressure desolventizing extremely to 200g ethyl acetate aqueous phase extracted Without cut, 11.4g compound 1-e are acquired, without the need for being further purified.
(6) preparation of compound 1-f：
The compound 1-e (11.4g, 30.0mmol) obtained in step (5) is added in 120g methanesulfonic acids, is protected in nitrogen Under shield, react 8.0 hours at 150～155 DEG C, while TLC tracking reaction process.After completion of the reaction, reaction system is toppled over Enter 800g frozen water and reaction is quenched, then system separates out a large amount of yellow solids, filtration under diminished pressure, filter cake ethanol rinse is obtained after being dried 9.6g compound 1-f, yield is 88.07%.
(7) preparation of compound 1-g：
Raw material 4,4'- di-t-butyls -2- bromo biphenyls (17.3g, 50.0mmol) are added in 100g THF solutions, in nitrogen Under gas shielded, -78 DEG C are cooled to, add in system and n-BuLi/hexane solution (20mL, 2.5mol/L) is added dropwise, -78 Insulation reaction 2.0 hours at DEG C, be then to slowly warm up to -20 DEG C it is stand-by.By the compound 1-f obtained in step (6) (9.1g, 200g THF 25.0mmol) are added to, heating for dissolving is in homogeneous phase, under nitrogen protection, at -20 DEG C, is slowly added dropwise To in the THF solution of above-mentioned 4,4'- di-t-butyls biphenyl lithium, insulated and stirred 2.0 hours is to slowly warm up to be stirred at room temperature 1.0 little When, 200g is poured into, in 2% watery hydrochloric acid, reaction is quenched, 300g ethyl acetate extraction, layering, saturated sodium carbonate is water-soluble Liquid is washed, saturated common salt water washing, organic phase decompression desolventizing to without cut, acquire 17.4g compound 1-g (containing part 4, 4'- di-t-butyl biphenyl), without the need for being further purified.
(8) preparation of compound 1-h：
By the compound 1-g (17.4g, 25.0mmol, the di-t-butyl biphenyl of 4,4'- containing part) obtained in step (7) and P-methyl benzenesulfonic acid (4.8g, 25mmol) is added in 150g toluene, and under nitrogen protection, system is slowly heated to 105～110 DEG C Lower reaction 3.0 hours, while TLC tracking reaction process.After completion of the reaction, 200g water quenchings are added to go out reaction, system layering, saturation Aqueous sodium carbonate is washed, water washing, to organic phase decompression desolventizing to without cut, then mixed with petroleum ether ethyl acetate Liquid carries out column chromatography purifying to residue, and wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Ethyl acetate=4:1, obtain 13.8g compound 1-h are obtained, yield is 90.19%.
(9) preparation of compound 1：
Compound 1-h (12.2g, 20.0mmol), phenyl boric acid (3.0g, 25mmol), the potassium carbonate that will be obtained in step (8) In (5.5g, 40mmol), water 20g and 180g toluene, under nitrogen protection, in system add palladium (135mg, 0.6mmol) with P (t-Bu)3·HBF4(296mg, 1.2mmol), reacts 7.0 hours at 85～88 DEG C, while TLC tracking is anti- Answer process.After completion of the reaction, system layering, from washing, to organic phase decompression desolventizing to without cut, then uses petroleum ether second Acetoacetic ester mixed liquor carries out column chromatography purifying to residue, and wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Acetic acid second Ester=20:1,10.5g compounds 1 are obtained, further crude product 320 DEG C of sublimation purifications in chemical gas-phase deposition system are obtained 9.4g white solid powders, yield is 71.75%.The compound, molecular formula C are recognized using HR-MS51H42, detected value [M]+=654.3286, calculated value 654.3287.
Embodiment 2The compound 8 that preparation is previously mentioned
(1) preparation of compound 8-a：
Take 36.1g compound 1-a (100.0mmol), 20.7g potassium carbonate (150mmol), the 80g obtained in step (1) Water, 22.3g phenyl boric acids (90mmol) and 300g toluene, under the protection of nitrogen, add catalyst 0.9g Pd (PPh3)4 (0.75mmol), backflow is then heated to, while tracking reaction process using thin-layered chromatography (TLC), has been reacted within about 6.0 hours Bi Hou, after being down to room temperature, system layering after then washing with water, by organic phase decompression desolventizing to without cut, then uses oil Ether acetic acid ethyl ester mixed liquor carries out column chromatography purifying to residue, and wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Second Acetoacetic ester=25:1,22.5g compound 8-a are obtained, yield is 59.84%.
(2) preparation of compound 8-b：
Take the bromo- 5- chlorine acenaphthylenes (100.0mmol) of raw material 23.1g 1-, the duplex of 14.7g potassium acetates (150mmol) 30.5 frequency that Alcohol borate (120mmol) is added in 250g toluene, under the protection of nitrogen, adds catalyst 0.8g Pd (dppf) Cl2 (1mmol), backflow is then heated to, fraction water device water-dividing is selected in course of reaction, while anti-using thin-layered chromatography (TLC) tracking Process is answered, about 5.0 hours after completion of the reaction, add 200g water, system layering, after then washing with water, by the anhydrous sulphur of organic phase Sour sodium is dried, and then toluene carries out column chromatography purifying, obtains 25.0g compound 8-b, and yield is 89.92%.
(3) preparation of compound 8-c：
Take the compound 8-b (12.5g, 45.0mmol) obtained in step (2), the compound 8-a for taking acquisition in step (1) (20.9g, 50.0mmol), 12.4g potassium carbonate (90mmol), 50g water and 200g toluene, under the protection of nitrogen, add catalysis Agent 0.5g Pd (PPh3)4(0.45mmol), backflow is then heated to, while reaction process is tracked using thin-layered chromatography (TLC), About 6.0 hours after completion of the reaction, and after being down to room temperature, organic phase after then washing with water, is reduced pressure desolventizing to nothing by system layering Cut, then obtains 17.6g compound 8-c with toluene ethyl alcohol recrystallization, and yield is 80.00%.
(4) preparation of compound 8-d：
By the compound 8-c (11.9g, 30.0mmol) obtained in step (3), NaOH (2.5g, 60mmol, 96%) And n-butanol 100g, under nitrogen protection, react 6.0 hours at 100～105 DEG C, while TLC tracking reaction process.Instead After should finishing, 200g water quenchings are added to go out reaction, twice, most at last organic phase reduces pressure desolventizing extremely to 200g ethyl acetate aqueous phase extracted Without cut, 14.2g compound 8-d are acquired, without the need for being further purified.
(5) preparation of compound 8-e：
The compound 8-d (14.2g, 30.0mmol) obtained in step (4) is added in 120g methanesulfonic acids, is protected in nitrogen Under shield, react 6.0 hours at 150～155 DEG C, while TLC tracking reaction process.After completion of the reaction, reaction system is toppled over Enter 1000g frozen water and reaction is quenched, then system separates out a large amount of yellow solids, filtration under diminished pressure, filter cake ethanol rinse is obtained after being dried 12.1g compound 8-e, yield is 88.32%.
(6) preparation of compound 8-f：
Raw material 4,4'- di-t-butyls -2- bromo biphenyls (17.3g, 50.0mmol) are added in 100g THF solutions, in nitrogen Under gas shielded, -78 DEG C are cooled to, add in system and n-BuLi/hexane solution (20mL, 2.5mol/L) is added dropwise, -78 Insulation reaction 2.0 hours at DEG C, be then to slowly warm up to -20 DEG C it is stand-by.By the compound 8-e obtained in step (5) (11.4g, 280g THF 25.0mmol) are added to, heating for dissolving is in homogeneous phase, under nitrogen protection, at -20 DEG C, is slowly added dropwise To in the THF solution of above-mentioned 4,4'- di-t-butyls biphenyl lithium, insulated and stirred 2.0 hours is to slowly warm up to be stirred at room temperature 1.0 little When, 200g is poured into, in 2% watery hydrochloric acid, reaction is quenched, 300g ethyl acetate extraction, layering, saturated sodium carbonate is water-soluble Liquid is washed, saturated common salt water washing, organic phase decompression desolventizing to without cut, acquire 19.3g compound 8-f (containing part 4, 4'- di-t-butyl biphenyl), without the need for being further purified.
(7) preparation of compound 8：
By the compound 8-f (18.1g, 25.0mmol, the di-t-butyl biphenyl of 4,4'- containing part) obtained in step (6) and P-methyl benzenesulfonic acid (4.8g, 25mmol) is added in 150g toluene, and under nitrogen protection, system is slowly heated to 105～110 DEG C Lower reaction 2.0 hours, while TLC tracking reaction process.After completion of the reaction, 200g water quenchings are added to go out reaction, system layering, saturation Aqueous sodium carbonate is washed, water washing, to organic phase decompression desolventizing to without cut, then mixed with petroleum ether ethyl acetate Liquid carries out column chromatography purifying to residue, and wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Ethyl acetate=15:1, obtain 13.8g compounds 8 are obtained, further crude product 320 DEG C of sublimation purifications in chemical gas-phase deposition system obtain 12.1g classes white Color pressed powder, yield is 68.75%.The compound, molecular formula C are recognized using HR-MS55H44, detected value [M]+= 704.3442, calculated value 704.3443.
Embodiment 3The compound 64 that preparation is previously mentioned
(1) preparation of compound 64-a：
At -10 DEG C and under the protection of nitrogen, the bromo- 1- hydroxy-2-naphthoic acids methyl esters of 28.1g 3- is taken (100.0mmol) it is dispersed in 200g dichloroethanes with 121.4g (120mmol) triethylamine, 31.0 TFMSs is then added dropwise Acid anhydride (110mmol), after completion of dropping, then reaction system is to slowly warm up to room temperature by insulation reaction 2.0 hours, then will be above-mentioned System is poured in 200g water, stirring reaction 30min, and system layering is washed from water, most at last organic phase decompression precipitation Agent acquires 41.3g compound 64-a, without the need for being further purified to without cut.
(2) preparation of compound 64-b：
Take 41.3g compound 64-a (100.0mmol), 20.7g potassium carbonate (150mmol), the 80g obtained in step (1) Water, 16.0g phenyl boric acids (90mmol) and 200g toluene, under the protection of nitrogen, add catalyst 0.9g Pd (PPh3)4 (0.75mmol), backflow is then heated to, while tracking reaction process using thin-layered chromatography (TLC), has been reacted within about 4.0 hours Bi Hou, after being down to room temperature, system layering after then washing with water, by organic phase decompression desolventizing to without cut, then uses oil Ether acetic acid ethyl ester mixed liquor carries out column chromatography purifying to residue, and wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Second Acetoacetic ester=5:1,21.5g compound 64-b are obtained, yield is 60.22%.
(3) preparation of compound 64-c：
Take the bromo- 6- chlorine acenaphthylenes (100.0mmol) of raw material 26.5g 1-, the duplex of 14.7g potassium acetates (150mmol) 30.5 frequency that Alcohol borate (120mmol) is added in 250g toluene, under the protection of nitrogen, adds catalyst 0.8g Pd (dppf) Cl2 (1mmol), backflow is then heated to, fraction water device water-dividing is selected in course of reaction, while anti-using thin-layered chromatography (TLC) tracking Process is answered, about 8.0 hours after completion of the reaction, add 200g water, system layering, after then washing with water, by the anhydrous sulphur of organic phase Sour sodium is dried, and then toluene carries out column chromatography purifying, obtains 26.3g compound 64-c, and yield is 84.03%.
(4) preparation of compound 64-d：
Take the compound 64-b (17.9g, 45.0mmol) obtained in step (2), the compound for taking acquisition in step (3) 64-c (15.6g, 50.0mmol), 12.4g potassium carbonate (90mmol), 50g water and 140g toluene, under the protection of nitrogen, add Catalyst 0.5g Pd (PPh3)4(0.45mmol), backflow is then heated to, while reacting using thin-layered chromatography (TLC) tracking Process, about 9.0 hours after completion of the reaction, and after being down to room temperature, system layering after then washing with water, organic phase is reduced pressure precipitation Then agent obtains 17.2g compound 64-d to without cut with toluene ethyl alcohol recrystallization, and yield is 76.12%.
(5) preparation of compound 64-e：
By the compound 64-d (15.1g, 30.0mmol) obtained in step (4), NaOH (2.5g, 60mmol, 96%) and n-butanol 100g, under nitrogen protection, react 12.0 hours at 100～105 DEG C, at the same TLC tracking react into Journey.After completion of the reaction, 200g water quenchings are added to go out reaction, twice, most at last organic phase decompression takes off 200g ethyl acetate aqueous phase extracted Solvent acquires 14.6g compound 64-e, without the need for being further purified to without cut.
(6) preparation of compound 1-f：
The compound 64-e (14.6g, 30.0mmol) obtained in step (5) is added in 140g methanesulfonic acids, in nitrogen Under protection, react 6.5 hours at 150～155 DEG C, while TLC tracking reaction process.After completion of the reaction, reaction system is inclined Pour 1000g frozen water into and reaction is quenched, then system separates out a large amount of yellow solids, filtration under diminished pressure, filter cake ethanol rinse is obtained after being dried To 12.7g compound 64-f, yield is 90.07%.
(7) preparation of compound 64-g：
Raw material 2- bromo biphenyls (11.7g, 50.0mmol) is added in 100g THF solutions, under nitrogen protection, cooling To -78 DEG C, add in system and n-BuLi/hexane solution (20mL, 2.5mol/L), the insulation reaction at -78 DEG C is added dropwise 2.0 hours, be then to slowly warm up to -20 DEG C it is stand-by.The compound 64-f (11.8g, 25.0mmol) obtained in step (6) is added Enter to 200g THF, heating for dissolving is in homogeneous phase, under nitrogen protection, at -20 DEG C, is slowly dropped to above-mentioned 2- biphenyl In the THF solution of lithium, insulated and stirred 2.0 hours is to slowly warm up to be stirred at room temperature 1.0 hours, is poured into 200g, 2% In watery hydrochloric acid, reaction is quenched, 300g ethyl acetate extraction, layering, saturated aqueous sodium carbonate is washed, saturated common salt water washing, Organic phase decompression desolventizing acquires 16.3g compound 64-g (biphenyl containing part), without the need for being further purified to without cut.
(8) preparation of compound 64-h：
By the compound 64-g (16.3g, 25.0mmol, biphenyl containing part) obtained in step (7) and p-methyl benzenesulfonic acid (4.8g, 25mmol) is added in 150g toluene, and under nitrogen protection, system reacts 1.0 at being slowly heated to 105～110 DEG C Hour, while TLC tracking reaction process.After completion of the reaction, 200g water quenchings are added to go out reaction, system layering, saturated sodium carbonate water Solution is washed, water washing, to organic phase decompression desolventizing to without cut, then with petroleum ether ethyl acetate mixtures to residual Thing carries out column chromatography purifying, and wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Ethyl acetate=25:1, acquire 13.3g compound 64-h, yield is 87.50%.
(9) preparation of compound 64：
Compound 64-h (12.1g, 20.0mmol), (10- (pyridine -2- bases) anthracene -9- bases) boron that will be obtained in step (8) In sour (7.5g, 25mmol), potassium carbonate (5.5g, 40mmol), water 20g and 300g toluene, under nitrogen protection, add in system Enter palladium (135mg, 0.6mmol) and P (t-Bu)3·HBF4(296mg, 1.2mmol), reaction 5.0 is little at 85～88 DEG C When, while TLC tracking reaction process.After completion of the reaction, system layering, from washing, evaporates organic phase decompression desolventizing to nothing Point, then column chromatography is carried out to residue with petroleum ether ethyl acetate mixtures and purified, wherein petroleum ether and ethyl acetate volume Than for petroleum ether：Ethyl acetate=10:1,11.5g compounds 64 are obtained, further crude product is in chemical gas-phase deposition system 360 DEG C of sublimation purifications, obtain 9.6g white solid powders, and yield is 58.18%.The compound is recognized using HR-MS, point Minor C64H43N, detected value [M]+=825.3395, calculated value 825.3396.
Embodiment 4The compound 80 that preparation is previously mentioned
(1) preparation of compound 80-a：
At -5 DEG C and under the protection of nitrogen, take the bromo- 3- hydroxynaphthoic acids methyl esters (100.0mmol) of 28.1g 2- and 121.4g (120mmol) triethylamine is dispersed in 200g dichloroethanes, and 31.0 trifluoromethanesulfanhydride anhydrides (110mmol) are then added dropwise, After completion of dropping, then reaction system is to slowly warm up to room temperature by insulation reaction 2.0 hours, then above-mentioned system is poured into In 200g water, stirring reaction 30min, system layering is washed from water, and most at last organic phase decompression desolventizing evaporates to nothing Point, 41.6g dark oil compounds 80-a are acquired, without the need for being further purified.
(2) preparation of compound 80-b：
Take 41.3g compound 80-a (100.0mmol), 20.7g potassium carbonate (150mmol), the 80g obtained in step (1) Water, 23.6g phenyl boric acids (95mmol) and 250g toluene, under the protection of nitrogen, add catalyst 0.58g Pd (PPh3)4 (0.5mmol), backflow is then heated to, while tracking reaction process using thin-layered chromatography (TLC), has been reacted within about 4.0 hours Bi Hou, after being down to room temperature, system layering after then washing with water, by organic phase decompression desolventizing to without cut, then uses oil Ether acetic acid ethyl ester mixed liquor carries out column chromatography purifying to residue, and wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Second Acetoacetic ester=7:1,28.0g compound 80-b are obtained, yield is 63.06%.
(3) preparation of compound 80-c：
Take the compound 80-b (23.4g, 50.0mmol) of acquisition in step (2), take acquired compound 1-c (15.6g, 50.0mmol), 13.8g potassium carbonate (100mmol), 100g water and 250g toluene, under the protection of nitrogen, addition is urged Agent 0.58g Pd (PPh3)4(0.50mmol), then be heated to backflow, while using thin-layered chromatography (TLC) tracking react into Journey, about 6.0 hours after completion of the reaction, and after being down to room temperature, system layering after then washing with water, organic phase is reduced pressure desolventizing To without cut, then 20.0g compound 80-c are obtained with toluene ethyl alcohol recrystallization, yield is 69.80%.
(4) preparation of compound 80-d：
By the compound 80-d (17.2g, 30.0mmol) obtained in step (3), potassium hydroxide (6.2g, 60mmol, 90%) and sec-butyl alcohol 200g, under nitrogen protection, react 6.0 hours at 110～120 DEG C, at the same TLC tracking react into Journey.After completion of the reaction, 200g water quenchings are added to go out reaction, twice, most at last organic phase decompression takes off 200g ethyl acetate aqueous phase extracted Solvent acquires 16.8g compound 80-d, without the need for being further purified to without cut.
(5) preparation of compound 80-e：
The compound 80-d (16.8g, 30.0mmol) obtained in step (4) is added in 100g methanesulfonic acids, in nitrogen Under protection, react 4.0 hours at 150～155 DEG C, while TLC tracking reaction process.After completion of the reaction, reaction system is inclined Pour 1000g frozen water into and reaction is quenched, then system separates out a large amount of yellow solids, filtration under diminished pressure, filter cake ethanol rinse is obtained after being dried To 14.3g compound 80-e, yield is 88.27%.
(6) preparation of compound 80-f：
Raw material 2- bromo biphenyls (11.7g, 50.0mmol) is added in 100g THF solutions, under nitrogen protection, cooling To -78 DEG C, add in system and n-BuLi/hexane solution (20mL, 2.5mol/L), the insulation reaction at -78 DEG C is added dropwise 2.0 hours, be then to slowly warm up to -20 DEG C it is stand-by.The compound 80-e (13.5g, 25.0mmol) obtained in step (5) is added Enter to 265g THF, heating for dissolving is in homogeneous phase, under nitrogen protection, at -20 DEG C, is slowly dropped to above-mentioned 2- biphenyl In the THF solution of lithium, insulated and stirred 2.0 hours is to slowly warm up to be stirred at room temperature 1.0 hours, is poured into 200g, 2% In watery hydrochloric acid, reaction is quenched, 500g ethyl acetate extraction, layering, saturated aqueous sodium carbonate is washed, saturated common salt water washing, Organic phase decompression desolventizing acquires 19.9g compound 80-f (biphenyl containing part), without the need for being further purified to without cut.
(7) preparation of compound 80-g：
By the compound 80-f (19.9g, 25.0mmol, biphenyl containing part) obtained in step (6) and p-methyl benzenesulfonic acid (1.0g, 5mmol) is added in 250g toluene, and under nitrogen protection, reaction 4.0 is little at system is slowly heated to 105～110 DEG C When, while TLC tracking reaction process.After completion of the reaction, 200g water quenchings are added to go out reaction, system layering, saturated sodium carbonate is water-soluble Liquid is washed, water washing, to organic phase decompression desolventizing to without cut, then with petroleum ether ethyl acetate mixtures to residue Column chromatography purifying is carried out, wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Ethyl acetate=6:1, acquire 15.1gization Compound 80-g, yield is 89.35%.
(8) preparation of compound 80：
By the compound 80-g (13.5g, 20.0mmol) obtained in step (7), 3- fluoranthene boronic acids (6.2g, 25mmol), In potassium carbonate (5.5g, 40mmol), water 40g and 120g toluene, under nitrogen protection, in system add palladium (135mg, 0.6mmol) with P (t-Bu)3·HBF4(296mg, 1.2mmol), reacts 5.0 hours at 85～88 DEG C, while TLC tracking is anti- Answer process.After completion of the reaction, system layering, from washing, to organic phase decompression desolventizing to without cut, then uses petroleum ether second Acetoacetic ester mixed liquor carries out column chromatography purifying to residue, and wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Acetic acid second Ester=12:1,14.1g compounds 80 are obtained, further crude product 360 DEG C of sublimation purifications in chemical gas-phase deposition system are obtained 11.3g light yellow solid powder, yield is 66.86%.The compound, molecular formula C are recognized using HR-MS67H38, detected value [M]+=842.2974, calculated value 842.2974.
Embodiment 5The compound 98 that preparation is previously mentioned
(1) preparation of compound 98-a：
At -15 DEG C and under the protection of nitrogen, the bromo- 4- hydroxy-2-naphthoic acids methyl esters of 28.1g 1- is taken (100.0mmol) it is dispersed in 200g dichloroethanes with 121.4g (120mmol) triethylamine, 31.0 TFMSs is then added dropwise Acid anhydride (110mmol), after completion of dropping, then reaction system is to slowly warm up to room temperature by insulation reaction 2.0 hours, then will be above-mentioned System is poured in 200g water, stirring reaction 30min, and system layering is washed from water, most at last organic phase decompression precipitation Agent acquires dark oil thing 41.4g, as compound 98-a, without the need for being further purified to without cut.
(2) preparation of compound 98-b：
Take 41.4g compound 98-a (100.0mmol), 20.7g potassium carbonate (150mmol), the 120g obtained in step (1) Water, 31.3g phenyl boric acids (90mmol) and 230g toluene, under the protection of nitrogen, add catalyst 0.9g Pd (PPh3)4 (0.75mmol), backflow is then heated to, while tracking reaction process using thin-layered chromatography (TLC), has been reacted within about 5.0 hours Bi Hou, after being down to room temperature, system layering after then washing with water, by organic phase decompression desolventizing to without cut, then uses oil Ether acetic acid ethyl ester mixed liquor carries out column chromatography purifying to residue, and wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Second Acetoacetic ester=5:1,30.1g compound 98-b are obtained, yield is 58.94%.
(3) preparation of compound 98-c：
Take the compound 98-b (25.5g, 45.0mmol) of acquisition in step (2), take acquired compound 64-c (15.6g, 50.0mmol), 12.4g potassium carbonate (90mmol), 100g water and 250g toluene, under the protection of nitrogen, add catalysis Agent 0.5g Pd (PPh3)4(0.45mmol), backflow is then heated to, while reaction process is tracked using thin-layered chromatography (TLC), About 9.0 hours after completion of the reaction, and after being down to room temperature, organic phase after then washing with water, is reduced pressure desolventizing to nothing by system layering Cut, then obtains 23.3g compound 98-c with toluene ethyl alcohol recrystallization, and yield is 76.89%.
(4) preparation of compound 98-d：
By the compound 98-c (20.2,30.0mmol) obtained in step (3), potassium hydroxide (6.2g, 60mmol, 90%) And n-butanol 120g, under nitrogen protection, react 12.0 hours at 120～125 DEG C, while TLC tracking reaction process.Instead After should finishing, 200g water quenchings are added to go out reaction, twice, most at last organic phase reduces pressure desolventizing extremely to 200g ethyl acetate aqueous phase extracted Without cut, 20.0g compound 98-d are acquired, without the need for being further purified.
(5) preparation of compound 98-e：
98-d 98-e
The compound 98-d (20.0g, 30.0mmol) obtained in step (4) is added in 160g methanesulfonic acids, in nitrogen Under protection, react 6.0 hours at 150～155 DEG C, while TLC tracking reaction process.After completion of the reaction, reaction system is inclined Pour 1000g frozen water into and reaction is quenched, then system separates out a large amount of yellow solids, filtration under diminished pressure, filter cake ethanol rinse is obtained after being dried To 17.7g compound 98-e, yield is 92.18%.
(6) preparation of compound 98-f：
Raw material 2- bromo biphenyls (11.7g, 50.0mmol) is added in 100g THF solutions, under nitrogen protection, cooling To -78 DEG C, add in system and n-BuLi/hexane solution (20mL, 2.5mol/L), the insulation reaction at -78 DEG C is added dropwise 2.0 hours, be then to slowly warm up to -20 DEG C it is stand-by.The compound 98-e (16.0,25.0mmol) obtained in step (5) is added Enter to 250g THF, heating for dissolving is in homogeneous phase.Under nitrogen protection, at -20 DEG C, it is slowly dropped to above-mentioned 2- biphenyl In the THF solution of lithium, insulated and stirred 2.0 hours is to slowly warm up to be stirred at room temperature 1.0 hours, is poured into 200g, 2% In watery hydrochloric acid, reaction is quenched, 250g ethyl acetate extraction, layering, saturated aqueous sodium carbonate is washed, saturated common salt water washing, Organic phase decompression desolventizing acquires 22.3g compound 98-f (biphenyl containing part), without the need for being further purified to without cut.
(7) preparation of compound 98-g：
By the compound 98-f (22.3g, 25.0mmol, biphenyl containing part) obtained in step (6) and p-methyl benzenesulfonic acid (0.5g, 2.5mmol) is added in 150g toluene, and under nitrogen protection, system reacts 6.0 at being slowly heated to 105～110 DEG C Hour, while TLC tracking reaction process.After completion of the reaction, 200g water quenchings are added to go out reaction, system layering, saturated sodium carbonate water Solution is washed, water washing, to organic phase decompression desolventizing to without cut, then with petroleum ether ethyl acetate mixtures to residual Thing carries out column chromatography purifying, and wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Ethyl acetate=8:1, acquire 16.8g Compound 98-g, yield is 86.60%.
(8) preparation of compound 98：
Compound 98-g (15.5g, 20.0mmol), phenyl boric acid (3.0g, 25mmol), the carbonic acid that will be obtained in step (7) In potassium (5.5g, 40mmol), water 40g and 280g toluene, under nitrogen protection, in system add palladium (135mg, 0.6mmol) with P (t-Bu)3·HBF4(296mg, 1.2mmol), reacts 5.0 hours at 85～88 DEG C, while TLC tracking is anti- Answer process.After completion of the reaction, system layering, from washing, to organic phase decompression desolventizing to without cut, then uses petroleum ether second Acetoacetic ester mixed liquor carries out column chromatography purifying to residue, and wherein petroleum ether and ethyl acetate volume ratio are petroleum ether：Acetic acid second Ester=6:1,13.5g compounds 98 are obtained, further crude product 360 DEG C of sublimation purifications in chemical gas-phase deposition system are obtained 9.9g white solid powders, yield is 60.36%.The compound, molecular formula C are recognized using HR-MS65H38, detected value [M]+=818.2973, calculated value 818.2974.
According to the method prepare compound 1 described in embodiment 1, embodiment 2, embodiment 3, embodiment 4 or embodiment 5 ～99, carry out detection compound using high resolution mass spec (HR-MS), then detect the detected value [M] that each compound is obtained+And Calculated value is as shown in Table 1 below.
Table 1
From the data of above-mentioned table 1 it is known that the present invention have successfully been obtained the organic photoelectrical material shown in Formulas I.
The compounds of this invention in luminescent device, as emitting layer material.To the compounds of this invention 1, compound 8, chemical combination Thing 64, compound 80,98 and current material BH1, BH2 carry out the test of hot property, and test result is as shown in table 2.
The heat stability testing of table 2
Note：Vitrification point Tg is by differential scanning calorimetry (DSC, German Nai Chi companies DSC204F1 differential scanning calorimetries Instrument) determine, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is in nitrogen atmosphere weightless 0.5% temperature, in Japanese Shimadzu It is measured on the TGA-50H thermogravimetric analyzers of company, nitrogen flow is 20mL/min；Highest occupied molecular orbital HOMO energy levels And minimum occupied molecular orbital lumo energy is by photoelectron emissions spectrometer (AC-2 types PESA) and ultraviolet specrophotometer (UV) measuring and calculation gained, tests as atmospheric environment.
From upper table data, there is the compound that the present invention is provided suitable HOMO, lumo energy to be suitable as OLED In device as Blue-light emitting host material material；The compound that the present invention is provided in upper table has higher heat endurance so that The made OLED life-span upgrading containing the compounds of this invention.
Embodiment two prepares organic electroluminescence device (hereinafter referred to as device)
In following embodiments for preparing organic electroluminescence device, used reagent material is as follows：
In embodiment two, by PR655 spectral scan radiancy meters and U.S. Keithley Soure Meter 2400 The test system of composition synchronizes driving voltage, quantum efficiency, the electricity that measurement detection obtains all devices to the device of gained Stream efficiency, power efficiency and brightness, wherein above-mentioned all measurements are carried out in atmosphere at room temperature.
Embodiment 1The preparation of device 1
A) anode cleaned on transparent substrate layer：Respectively deionized water, acetone, ethanol are respectively cleaned by ultrasonic 15 minutes, so Process 2 minutes in plasma cleaner afterwards；
B) the vacuum evaporation Hat-CN on anode, obtains hole injection layer compound, and the thickness of hole injection layer is 50nm；
C) on hole injection layer, NPB is deposited with by vacuum evaporation mode and obtains hole transmission layer, the thickness of hole transmission layer Spend for 10nm；
The mass ratio of compound and dopant material BD1 that present invention offer d) is deposited with hole transmission layer is compound 1： BD1=40:2, luminescent layer is obtained, the thickness of luminescent layer is 40nm；
E) on luminescent layer, vacuum evaporation BPhen obtains electron transfer layer, and the thickness of electron transfer layer is 30nm；
F) on the electron transport layer, vacuum evaporation LiF obtains electron injecting layer, and the thickness of electron injecting layer is 0.5nm；
G) on electron injecting layer, vacuum evaporation negative electrode Al, the thickness of negative electrode is 100nm, obtains device 1.
After electroluminescent device accomplished as described above, the driving voltage of measurement device, quantum efficiency, current efficiency, power effect Rate and brightness, its result is in table 3.
Embodiment 2The preparation of device 2
The present embodiment is with the difference of device 1：Preparing the luminescent layer material of main part of organic electroluminescence device makes With compound provided by the present invention 8.
Embodiment 3The preparation of device 3
The present embodiment is with the difference of device 1：The luminescent layer material of main part of the organic electroluminescence device of preparation Using compound provided by the present invention 64.
Embodiment 4The preparation of device 4
The present embodiment is with the difference of device 1：The luminescent layer material of main part of the organic electroluminescence device of preparation Using compound provided by the present invention 80.
Embodiment 5The preparation of device 5
The present embodiment is with the difference of device 1：The luminescent layer material of main part of the organic electroluminescence device of preparation Using compound provided by the present invention 98.
Comparative example 1The preparation of device 1#
Unlike device comparative example 1 and device 1：The luminescent layer of organic electroluminescence device is with mass ratio as material of main part BH1：Dopant material BD1=40:2 are deposited with.
Comparative example 2The preparation of device 2#
Unlike device comparative example 2 and device 1：The luminescent layer of organic electroluminescence device is with mass ratio as material of main part BH2：Dopant material BD1=40:2 are deposited with.
Comparative example 3The preparation of device 3#
Unlike device comparative example 3 and device 1：The luminescent layer of organic electroluminescence device is with mass ratio as material of main part BH1：Dopant material BD2=40:2 are deposited with.
Comparative example 4The preparation of device 4#
Unlike device comparative example 4 and device 1：The luminescent layer of organic electroluminescence device is with mass ratio as material of main part BH2：Dopant material BD2=40:2 are deposited with.
Correlated results is obtained as shown in Table 3 below to device 1～5 and device 1#～4# detections：
Table 3
By above-mentioned table 3 it is known that organic photoelectrical material provided by the present invention can be applicable to organic electroluminescence device, And allow organic electroluminescence device to obtain good performance.Material of the present invention sending out as electroluminescent device Photosphere material of main part is used, then the driving voltage of organic electroluminescence device is below existing conventional BH1 and BH2 as luminous The device 1# and 2# of layer main body material.
In addition, comparing with 4# with device 1#, 2#, 3#, quantum efficiency, current efficiency, the power of the device that the present invention is provided Efficiency and brightness are obviously improved.
The announcement of book according to the above description, the application those skilled in the art can also be carried out to above-mentioned embodiment Appropriate change and modification.Therefore, the application is not limited to specific embodiment disclosed and described above, to the application's Some modifications and changes should also be as falling in the protection domain of claims hereof.

Claims (10)

1. a kind of volution organic photoelectrical material, it is characterised in that its formula is as shown in formula I or Formula II：
Wherein, R1、R2Be each independently selected from hydrogen-based, halogen, cyano group, nitro, isothiocyano, sulfonyl, sulfoxide group, amide groups, Carbon number is 1～10 alkyl and the one kind in alkoxyl that substituted or unsubstituted carbon number is 1～12；A is selected from It is a kind of in phenylene or naphthylene；Ar1、Ar2It is each independently selected from hydrogen-based, deuterium base, fluorine-based, chloro, cyano group, phenyl, carbon atom Number for 7～14 benzene alkyl, the conjugated polycyclic aryl that carbon number is 10～60 and containing N, S, O in it is at least one Carbon number is the one kind in 12～60 aromatic heterocyclic radicals.
2. volution organic photoelectrical material according to claim 1, it is characterised in that its formula is represented such as by III～Formula X of formula Under：
3. volution organic photoelectrical material according to claim 1 and 2, it is characterised in that the Ar1、Ar2Independently of one another One kind in following radicals：
4. volution organic photoelectrical material according to claim 3, it is characterised in that its chemical structural formula is as follows：
5. a kind of preparation method of the volution organic photoelectrical material any one of Claims 1 to 4, it is characterised in that bag Include following steps：
1) with raw material 1 and trifluoromethanesulfanhydride anhydride as raw material, the reaction under the conditions of inert atmosphere neutral and alkali generates intermediate 1；
2) step 1) in the basic conditions reaction generates intermediate 2 under catalyst action for the intermediate 1 and the aryl boric acid that obtain；
3) with raw material 2 and duplex pinacol borate as raw material, the reaction under catalyst action under alkalescence condition obtains intermediate 3, catalyst is selected from Pd (dppf) Cl2、Pd(PPh3)2Cl2In one kind；
4) by step 2) in the intermediate 2 and the step 3 that obtain) in obtained by intermediate 3 urge under the conditions of inert atmosphere neutral and alkali Reaction under agent catalytic action generates intermediate 4；
5) by step 4) in gained intermediate 4 there is ester hydrolysis reaction under inert gas shielding under alkalescence condition, contained There is the reaction system of intermediate 5；
6) by step 5) in obtain intermediate 5 react in acidic organic solvent under inert gas shielding generate intermediate 6；
7) occur after substitution reaction, in the reaction system under inert gas shielding as raw material with raw material 3 and organolithium reagent Add step 6) in obtain intermediate 6 organic solution, obtain the reaction system containing intermediate 7；
8) by step 7) in the intermediate 7 of gained react in aromatic hydrocarbon solvent under inert gas shielding with raw material 4 and contained The reaction system of intermediate 8, the raw material 4 is one or more in P-TOLUENE SULFO ACID 99, methanesulfonic acid and trifluoroacetic acid；
9) by step 8) in the intermediate 8 and the aryl bromo-derivative Ar that obtain2- Br under inert gas shielding, catalyst and alkaline bar Volution organic photoelectrical material is obtained under part effect in reaction；
Wherein, step 2), 4), 9) described in catalyst be selected from Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2And Pd2(dba)3 In one or more；
Synthetic route is as follows：
6. the preparation method of volution organic photoelectrical material according to claim 5, it is characterised in that comprise the steps：
1) under the protection of inert gas and under -20～30 DEG C of temperature conditionss, by trifluoromethanesulfanhydride anhydride be added to containing Reacted in the organic solution of raw material 1 and triethylamine, obtained the reaction system containing intermediate 1；
2) by step 1) middle intermediate 1, the aryl boric acid Ar for obtaining1-B(OH)2, alkaline substance solution and catalyst are added has In machine solvent, react 2～24 hours under the protection of inert gas and at 0～90 DEG C, obtain the reaction containing intermediate 2 System；
3) raw material 2, duplex pinacol borate, catalyst and alkaline matter are added to into toluene, dimethylbenzene, trimethylbenzene, N, N- In dimethylformamide or dimethyl acetamide, under the protection of inert gas and at 0～150 DEG C, reaction 2～24 is little When, obtain the reaction system containing intermediate 3；
4) by step 3) in obtain intermediate 3, step 2) in obtain intermediate 2, alkaline substance solution and catalyst add In entering organic solvent, react 2～24 hours under the protection of inert gas and at 0～90 DEG C, obtain containing intermediate 4 Reaction system；
5) by step 4) in obtain intermediate 4 and alkaline matter add organic solvent in, under the protection of inert gas and React 2～24 hours at 0～130 DEG C, obtain the reaction system containing intermediate 5；
6) by step 5) in obtain intermediate 5 add organic solvent in, under the protection of inert gas and at 0～150 DEG C Lower reaction 2～24 hours, obtains the reaction system containing intermediate 6；
7) under the protection of inert gas and under -100～0 DEG C of temperature conditionss, organolithium reagent is added to containing former Reacted in the organic solution of material 3, backward reaction system in add the organic solution of the intermediate 6 of acquisition in step (6), Obtain the reaction system containing intermediate 7；
8) by step 7) in obtain intermediate 7 and raw material 4 be added in organic solvent, under the protection of inert gas and At 0～150 DEG C, react 2～24 hours, obtain the reaction system containing intermediate 8；
9) will be in step 8) middle intermediate 8, the aryl bromo-derivative Ar for obtaining2- Br, alkaline substance solution and catalyst are added to be had In machine solvent, react 2～24 hours under the protection of inert gas and at 0～90 DEG C, obtain the organic photoelectric of the present invention Material.
7. the preparation method of organic photoelectrical material according to claim 6, it is characterised in that in the step 1) in, will In dichloroethanes, the addition of trifluoromethanesulfanhydride anhydride causes trifluoromethanesulfanhydride anhydride with raw material 1 for raw material 1 and triethylamine Monodispersed Mol ratio be trifluoromethanesulfanhydride anhydride：Raw material 1=1～1.2：1, triethylamine is triethylamine with the mol ratio of raw material 1：Raw material 1=1 ～1.5:1；
In the step 2) in, the aryl boric acid Ar1-B(OH)2Addition for cause aryl boric acid Ar1-B(OH)2With it is described The mol ratio of intermediate 1 is aryl boric acid Ar1-B(OH)2：Intermediate 1=0.5～1.0:1.0, the addition of the catalyst is So that catalyst is 0.001～0.1 with the mol ratio of intermediate 1:1.
In the step 3) in, the addition of duplex pinacol borate cause duplex pinacol borate and raw material 2 mole The ratio of amount is duplex pinacol borate：Raw material 2=1～2：1；The addition of the catalyst is for so that catalyst and raw material 2 Mol ratio be 0.001～0.1:1.
In the step 4) in, the addition of the intermediate 3 be so that intermediate 3 is with the mol ratio of the intermediate 2 in Mesosome 3：Intermediate 2=1.0～2.0:1, the addition of the catalyst is so that catalyst is with the mol ratio of intermediate 2 0.001～0.1:1.
In the step 7) in, it is described by raw material 3 and the Monodispersed of intermediate 6 in tetrahydrofuran, the addition of organolithium reagent So that organolithium reagent is organolithium with the mol ratio of raw material 3：Raw material 3=1～1.2：1, raw material 3 and intermediate 6 mole Than for raw material 3：Intermediate 6=1～1.2:1.
In the step 8) in, it is raw material 4 with the ratio of the mole of intermediate 7 that the addition of raw material 4 causes raw material 4：Intermediate 7 =1～2：1.
In the step 9) in, the aryl bromo-derivative Ar2The addition of-Br is for so that aryl bromo-derivative Ar2- Br with it is described in The mol ratio of mesosome 8 is aryl bromo-derivative Ar2-Br：Intermediate 8=1.0～2.0:1, the addition of the catalyst is to cause Catalyst is 0.001～0.1 with the mol ratio of intermediate 8:1.
8. the preparation method of the volution organic photoelectrical material according to claim 6 or 7, it is characterised in that the basic species Matter is selected from one or more in potassium carbonate, sodium carbonate, potassium phosphate, potassium acetate, potassium hydroxide, NaOH.
9. the preparation method of the volution organic photoelectrical material according to claim 6 or 7, it is characterised in that step 2), 4), 9) organic solvent described in is selected from one or more in tetrahydrofuran, toluene, dioxane and dimethyl acetamide；
Step 5) described in one or more in n-butanol, sec-butyl alcohol, ethanol and the normal propyl alcohol of organic solvent；
Step 6) described in one kind in the methanesulfonic acid and TFMS of organic solvent；
Step 7) described in organic solvent be tetrahydrofuran；
Step 8) described in one or more in benzene, dimethylbenzene and the trimethylbenzene of organic solvent.
10. a kind of organic electroluminescence device, it is characterised in that be provided with least between the anode and negative electrode of the luminescent device Individual luminescent layer, organic photoelectrical material of the luminescent layer by any one of Claims 1 to 4 is made.
CN201610867745.7A 2016-09-29 2016-09-29 A kind of loop coil organic photoelectrical material and its preparation method and application Active CN106588531B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610867745.7A CN106588531B (en) 2016-09-29 2016-09-29 A kind of loop coil organic photoelectrical material and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610867745.7A CN106588531B (en) 2016-09-29 2016-09-29 A kind of loop coil organic photoelectrical material and its preparation method and application

Publications (2)

Publication Number Publication Date
CN106588531A true CN106588531A (en) 2017-04-26
CN106588531B CN106588531B (en) 2019-04-02

Family

ID=58556025

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610867745.7A Active CN106588531B (en) 2016-09-29 2016-09-29 A kind of loop coil organic photoelectrical material and its preparation method and application

Country Status (1)

Country Link
CN (1) CN106588531B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108821934A (en) * 2018-05-22 2018-11-16 石家庄诚志永华显示材料有限公司 A kind of compound and Organnic electroluminescent device and its material comprising the compound

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105131939A (en) * 2015-08-28 2015-12-09 中节能万润股份有限公司 Organic electroluminescence material with spiral structure and application thereof
CN105440004A (en) * 2015-11-10 2016-03-30 中节能万润股份有限公司 Organic electroluminescent material and application thereof
CN105778891A (en) * 2016-03-11 2016-07-20 中节能万润股份有限公司 Organic optoelectronic material, preparation method thereof and organic light emitting diode containing organic material
CN105968076A (en) * 2016-05-12 2016-09-28 中节能万润股份有限公司 Spiral organic electroluminescent material and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105131939A (en) * 2015-08-28 2015-12-09 中节能万润股份有限公司 Organic electroluminescence material with spiral structure and application thereof
CN105440004A (en) * 2015-11-10 2016-03-30 中节能万润股份有限公司 Organic electroluminescent material and application thereof
CN105778891A (en) * 2016-03-11 2016-07-20 中节能万润股份有限公司 Organic optoelectronic material, preparation method thereof and organic light emitting diode containing organic material
CN105968076A (en) * 2016-05-12 2016-09-28 中节能万润股份有限公司 Spiral organic electroluminescent material and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108821934A (en) * 2018-05-22 2018-11-16 石家庄诚志永华显示材料有限公司 A kind of compound and Organnic electroluminescent device and its material comprising the compound
CN108821934B (en) * 2018-05-22 2021-12-31 石家庄诚志永华显示材料有限公司 Compound, organic electroluminescent device containing compound and material thereof

Also Published As

Publication number Publication date
CN106588531B (en) 2019-04-02

Similar Documents

Publication Publication Date Title
CN105778891B (en) Organic photoelectrical material, preparation method and the organic electroluminescence device including the organic material
Tang et al. Highly efficient deep-blue electroluminescence based on the triphenylamine-cored and peripheral blue emitters with segregative HOMO–LUMO characteristics
JP6174819B2 (en) Heterocyclic compound and organic light emitting device using the same
Reghu et al. Air stable electron-transporting and ambipolar bay substituted perylene bisimides
KR101356953B1 (en) Carbazole derivatives and organic light emitting device using the same
EP3533798B1 (en) Dibenzopyrromethene boron chelate compound, near infrared light absorbing material, thin film, and organic electronic device
TW201638079A (en) Materials for electronic devices
EP2316906A2 (en) Anthracene derivatives and organic light-emitting device including the same
CN102224158A (en) Novel heterocyclic compound and use thereof
Chen et al. Deep blue organic light-emitting devices enabled by bipolar phenanthro [9, 10-d] imidazole derivatives
CN107954942B (en) Benzopyrazines replaces anthracene derivant and organic electroluminescence device
CN109467511A (en) A kind of aromatic amine compounds and its organic luminescent device
CN109293516A (en) A kind of tri-arylamine group compound and its organic luminescent device
Lee et al. Asymmetric indolylmaleimides as non-dopant type red color emitting dyes
Li et al. Two bipolar blue-emitting fluorescent materials based on 1, 3, 5-triazine and peripheral pyrene for organic light-emitting diodes
CN110835351A (en) Organic compound with pyrromethene boron complex as core and preparation and application thereof
TW201910339A (en) Dibenzopyrrolemethine boron chelate compound, near-infrared light absorbing material, film and organic electronic device
CN106588531B (en) A kind of loop coil organic photoelectrical material and its preparation method and application
CN106928016B (en) A kind of electroluminescent organic material and its preparation method and application containing spirane structure
Yang et al. New insight into intramolecular conjugation in the design of efficient blue materials: from the control of emission to absorption
EP2998380A1 (en) Compound for organic optoelectric device, organic light-emitting diode including same, display device including organic light-emitting diode
CN106478358B (en) A kind of organic photoelectrical material containing spirane structure and its application
Wang et al. A novel heteroterfluorene for efficient blue and white OLEDs
CN108203416A (en) Using fluorenes as the compound and organic electroluminescence device of core
CN109928961B (en) Photoelectric material containing 4-sulfosulfonyl aryl dibenzofuran and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant