CN104262347B - Blue-light semiconductor material containing two pyrazolo pyrenes and preparation method thereof and the organic luminescent device being made up of the material - Google Patents

Blue-light semiconductor material containing two pyrazolo pyrenes and preparation method thereof and the organic luminescent device being made up of the material Download PDF

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CN104262347B
CN104262347B CN201410438947.0A CN201410438947A CN104262347B CN 104262347 B CN104262347 B CN 104262347B CN 201410438947 A CN201410438947 A CN 201410438947A CN 104262347 B CN104262347 B CN 104262347B
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pyrazolo
pyrenes
blue
semiconductor material
pyrene
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CN104262347A (en
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尹恩心
林文晶
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Olide (Shanghai) Photoelectric Material Technology Co., Ltd.
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SHANGHAI KELI ENTE CHEMICAL MATERIALS Co Ltd
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Abstract

The present invention relates to a kind of blue-light semiconductor material for containing two pyrazolo pyrenes and preparation method thereof and the organic luminescent device being made up of the material, the unstable technical problem under long-time or high voltage condition of the device spectral that the existing pyrene class blue light material of solution is made.The blue-light semiconductor material containing two pyrazolo pyrenes that the present invention is provided is reacted by two pyrazolo pyrenes and the bromide containing R group, generates the two pyrazolo pyrene analog derivatives containing R substituent.The obtained blue-light semiconductor material for containing two pyrazolo pyrenes has high luminous efficiency, high luminous efficiency shows that the compound can be used as luminescent material or light emitting host material, especially can be used as phosphorescence blueness material of main part, for showing high efficiency, high brightness, long-life in organic electroluminescence device, relatively low have the advantages that manufacturing cost, reduce the manufacturing cost of organic electroluminescence device.

Description

Blue-light semiconductor material containing two pyrazolo pyrenes and preparation method thereof and by the material system The organic luminescent device for becoming
Technical field
The present invention relates to organic photoelectrical material field, and in particular to a kind of blue-light semiconductor material for containing two pyrazolo pyrenes and Its preparation method and the organic luminescent device being made up of the material.
Background technology
Organic electroluminescent El element hereinafter referred to as " organic EL device " typically by two opposed electrodes and is inserted in this At least one of which organic luminescent compounds composition between two electrodes.Electric charge is injected into having of being formed between the anode and cathode In machine layer, to form electronics and hole pair, the organic compound with fluorescence or phosphorescent characteristics is made to generate light transmitting.
Organic Light Emitting Diode OLED is a kind of new flat panel display device, steady with energy-conservation, fast response time, color Fixed, environmental suitability is strong, radiationless, life-span length, light weight, thickness of thin the features such as.Due to photoelectric communication and multimedia in recent years The developing rapidly of field, organic optoelectronic material has become the core of modern society's information and electronic industry.
For electroluminescent organic material research be from nineteen fifty Bernose to the macromolecule membrane containing organic pigment Apply the observation of high current voltage to start.Nineteen sixty-five, Pope et al. are found that the Electroluminescence Properties of anthracene single crystal first, and this is organic The first electro optical phenomenon of compound.1987, Tang of Kodak et al. find, formed by organic material with point Even if the organic luminescent device from function lamination can also provide 1000cd/cm under the low-voltage of 10V or less2Or higher height Brightness.
, due to having very high thermal stability, the excellent in efficiency of luminescence generated by light, used as OLED for pyrene and its derivative at present Material, increasingly paid close attention to by people, various efficiently red, green electroluminescent organic materials are constantly developed. Comparatively speaking, in efficiency, the aspect such as excitation and life-span is also more delayed for blue light material.Nan dian Yao device can be divided into electricity Photo-phosphorescence and two class of electroluminescent fluorescent.Although electroluminescent phosphorescence can reach the internal quantum efficiency for being close to 100%, dark blue luminous Seldom.As excitation is very sensitive to the concentration that adulterates, the precision of doping must control within the scope of ± 0.5wt%.Phase is divided From another the fatal shortcoming for being doping system, device spectral is can result in unstable under long-time or high voltage condition. Therefore, undoped blue light material and device comparatively speaking have certain advantage.
Content of the invention
The invention solves the problems that the device spectral that existing pyrene class blue light material is made is unstable under long-time or high voltage condition Fixed technical problem, provides a kind of blue-light semiconductor material for containing two pyrazolo pyrenes and preparation method thereof and is made up of the material Organic luminescent device.
In order to solve above-mentioned technical problem, technical scheme is specific as follows：
A kind of blue-light semiconductor material for containing two pyrazolo pyrenes, the structure expression of the material is：
In formula I, R represents aryl, substituted or unsubstituted carbon number of the substituted or unsubstituted carbon number for 10-20 Heteroaryl or triarylamine for 7-18.
In technique scheme, the described blue-light semiconductor material containing two pyrazolo pyrenes is for shown in following structural formula One kind in compound 1-20：
A kind of preparation method of the blue-light semiconductor material for containing two pyrazolo pyrenes, comprises the following steps：
Step S1：Two pyrazolo pyrene intermediates, the bromide containing R group, catalysis is added in the reaction vessel after degassing Agent, alkali and solvent；
Step S2：Rise high reaction temperature and flow back, fully react；
Step S3：Cooling, crosses silica gel funnel, washs, is spin-dried for, the blue-light semiconductor material being recrystallized to give containing two pyrazolo pyrenes Material.
In technique scheme, two pyrazolo pyrene intermediates described in step S1 be by 1,6- dimethyl pyrene through nitrification, Reduction, cyclization.
In technique scheme, reaction temperature described in step S2 is 110 DEG C, and the time that is flowed back is 24h.
A kind of organic luminescent device for making of blue-light semiconductor material by containing two pyrazolo pyrenes, it include first electrode, Second electrode and the one or more organic compound layers being placed between the first electrode and the second electrode, its are special Levy and be, organic compound layer described at least one includes the blue-light semiconductor material for containing two pyrazolo pyrenes.
Blue-light semiconductor material containing two pyrazolo pyrenes and preparation method thereof that the present invention is provided and it is made up of the material The beneficial effect of organic luminescent device is：
The blue-light semiconductor material containing two pyrazolo pyrenes of the present invention has relatively good hole, electron transfer rate, Two pyrazolo pyrene analog derivatives have big conjugate planes structure such that it is able to provide high electron mobility, and pyrazole group has There is relatively low reduction potential, beneficial to electronics is received, pyrazole group is introduced the both sides of pyrene, the electric charge of such compound can be improved Transfer ability so as to good electronic transmission performance.And the addition of both sides aromatic yl group, such compound can be reduced Coplanarity, so as to improve its film forming.Additionally, the symmetry of molecular structure can increase the regularity of molecular stacks, permissible Improve compound carrier mobility.Therefore the blue-light semiconductor material containing two pyrazolo pyrenes of the present invention has higher electronics Transmission performance, good film-forming property, there is preferable stability at room temperature, the device that is applied also has higher stability.
The blue-light semiconductor material containing two pyrazolo pyrenes of the present invention has high luminous efficiency, and high luminous efficiency shows The compound can be used as luminescent material or light emitting host material, especially can be as phosphorescence blueness material of main part, for organic Show in electroluminescent device high efficiency, high brightness, long-life, relatively low have the advantages that manufacturing cost, reduce Organic Electricity The manufacturing cost of electroluminescence device.
Specific embodiment
The present invention provide the blue-light semiconductor material containing two pyrazolo pyrenes be by two pyrazolo pyrenes and the bromination containing R group Thing reacts, and generates the two pyrazolo pyrene analog derivatives containing R substituent, and concrete synthetic route is as follows：
The specific preparation process of blue-light semiconductor material containing two pyrazolo pyrenes and condition as follows：
Step S1：Under nitrogen protection, two pyrazolo pyrene intermediates are added in the reaction vessel after degassing, contain R group Bromide, three (dibenzalacetone) two palladium, sodium tert-butoxide and tri-butyl phosphine, and dissolved with toluene；
Step S2：It is 110 DEG C and the 24h that flows back to rise high reaction temperature, fully reacts；
Step S3：Room temperature is cooled to, silica gel funnel is crossed, dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, Suction filtration, obtains the blue-light semiconductor material containing two pyrazolo pyrenes after drying.
Two pyrazolo pyrene intermediates described in step S1 be by 1,6- dimethyl pyrene through nitrification, reduction, cyclization. Concrete synthetic route is as follows：
The concrete preparation process of two pyrazolo pyrene intermediates and condition as follows：
In the 500mL there-necked flask equipped with reflux, the compound of input 0.100mol 1,6- dimethyl pyrene, 0 DEG C Under be added thereto to nitration mixture sulfuric acid：Nitric acid：Water=4：2：1140mL, is warming up to 30 DEG C afterwards, stands, use second after stirring 30min Upper strata itrated compound is extracted by acetoacetic ester, is washed with water to acidity is not shown, point liquid, revolving, recrystallization, is filtered to obtain product (III) 0.89mol, yield 89%.
The aqueous hydrochloric acid solution of 150mL 2moL/L is added in the 500mL there-necked flask equipped with reflux, lower Xu of stirring Xu adds the iron powder of 0.4moL and the compound of 0.1moL (III), and heating reflux reaction 3-8 hour, after reaction terminates, after cooling The saturated aqueous sodium carbonate for having prepared is added in reactant liquor to neutrality.It is extracted with ethyl acetate, point liquid, solvent is spin-dried for, does Dry, obtain product (IV) 0.95moL, yield 95%.
0.1moL compound (IV) is added in the 500mL there-necked flask equipped with reflux, be added thereto under ice bath 40mL concentrated hydrochloric acid and 50mL sodium nitrate, stirring reaction 30min, are added thereto to sodium fluoborate saturated solution, continue stirring 30min, filters, and dries, gained solid chemical compound is dissolved in chloroform, addition 0.5moL potassium acetate, stirring reaction 3-8h, TLC determines that reaction terminates, washing, point liquid, revolving, and recrystallization obtains two pyrazolo pyrene intermediate 0.86moL, yield 86%.
Understandable for enabling the above objects, features and advantages of the present invention to become apparent from, the concrete reality to the present invention below The mode of applying is described in detail.Elaborate a lot of details in order to fully understand the present invention in the following description.But The present invention can be implemented with being much different from alternate manner described here, and those skilled in the art can be without prejudice to this Similar improvement is done in the case of bright intension, and therefore the present invention is not limited by following public specific embodiment.
Embodiment 1：The synthesis of compound 1
Under nitrogen protection, by bromo- for two pyrazolo pyrene intermediate 100mmol, 9- 9H- carbazole 220mmol, three (two benzal Benzylacetone) two palladium 5mmol, sodium tert-butoxide 400mmol, tri-butyl phosphine 20mmol are put in reaction vessel, and use 500ml toluene Dissolving, 110 DEG C of back flow reaction 24h, reaction end is determined with thin-layer chromatography (TLC), reaction is finished, and is cooled to room temperature, crosses silica gel Funnel, dichloromethane are rinsed, and are spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 88mmol compound 1 after drying, receives Rate 88%.
Embodiment 2：The synthesis of compound 2
Under nitrogen protection, by two pyrazolo pyrene intermediate 100mmol, 2- bromonaphthalene 215mmol, three (dibenzalacetones) Two palladiums (5mmol), sodium tert-butoxide 409mmol, tri-butyl phosphine 20mmol are put in reaction vessel, and are dissolved with 500ml toluene, 110 DEG C of back flow reaction 24h, determine reaction end with thin-layer chromatography (TLC), and reaction is finished, and are cooled to room temperature, cross silica gel funnel, Dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 79mmol compound 2, yield after drying 79%.
Embodiment 3：The synthesis of compound 3
Under nitrogen protection, by two pyrazolo pyrene intermediate 102mmol, 3- bromine phenanthrene 219mmol, three (dibenzalacetones) Two palladium 5mmol, sodium tert-butoxide 404mmol, tri-butyl phosphine 20mmol are put in reaction vessel, and are dissolved with 500ml toluene, 110 DEG C of back flow reaction 24h, determine reaction end with thin-layer chromatography (TLC), and reaction is finished, and are cooled to room temperature, cross silica gel funnel, Dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 74mmol compound 3, yield after drying 73%.
Embodiment 4：The synthesis of compound 4
Under nitrogen protection, by bromo- for two pyrazolo pyrene intermediate 104mmol, 2- 4,7- phenanthroline 217mmol, three (two BENZYLIDENE ACETONE) two palladium 5.1mmol, sodium tert-butoxide 405mmol, tri-butyl phosphine 20mmol are put in reaction vessel, are used in combination 500ml toluene dissolves, and 110 DEG C of back flow reaction 24h determine reaction end with thin-layer chromatography (TLC), and reaction is finished, and is cooled to room Temperature, crosses silica gel funnel, and dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 82mmolization after drying Compound 4, yield 79%.
Embodiment 5：The synthesis of compound 5
Under nitrogen protection, by two pyrazolo pyrene intermediate 104mmol, 3- bromoquinoline 221mmol, three (dibenzylidenes third Ketone) two palladium 5.3mmol, sodium tert-butoxide 410mmol, tri-butyl phosphine 19mmol be put in reaction vessel, and molten with 500ml toluene Solution, 110 DEG C of back flow reaction 24h, reaction end is determined with thin-layer chromatography (TLC), reaction is finished, and is cooled to room temperature, crosses silica gel leakage Bucket, dichloromethane are rinsed, and are spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 80mmol compound 5, yield after drying 77%.
Embodiment 6：The synthesis of compound 6
Under nitrogen protection, by two pyrazolo pyrene intermediate 100mmol, 9- bromine anthracene 221mmol, three (dibenzalacetones) Two palladium 5.6mmol, sodium tert-butoxide 400mmol, tri-butyl phosphine 20mmol are put in reaction vessel, and are dissolved with 500ml toluene, 110 DEG C of back flow reaction 24h, determine reaction end with thin-layer chromatography (TLC), and reaction is finished, and are cooled to room temperature, cross silica gel funnel, Dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 86mmol compound 6, yield after drying 86%.
Embodiment 7：The synthesis of compound 7
Under nitrogen protection, by two pyrazolo pyrene intermediate 101mmol, 3- bromine fluoranthene 221mmol, three (dibenzylidenes third Ketone) two palladium 5.1mmol, sodium tert-butoxide 410mmol, tri-butyl phosphine 20mmol be put in reaction vessel, and molten with 500ml toluene Solution, 110 DEG C of back flow reaction 24h, reaction end is determined with thin-layer chromatography (TLC), reaction is finished, and is cooled to room temperature, crosses silica gel leakage Bucket, dichloromethane are rinsed, and are spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 78mmol compound 7, yield after drying 77%.
Embodiment 8：The synthesis of compound 8
Under nitrogen protection, by bromo- for two pyrazolo pyrene intermediate 100mmol, 2- 1- phenyl -1H- benzo [d] imidazoles 220mmol, three (dibenzalacetone) two palladium 5.0mmol, sodium tert-butoxide 409mmol, tri-butyl phosphine 20mmol are put into reaction In container, and dissolved with 500ml toluene, 110 DEG C of back flow reaction 24h, reaction end is determined with thin-layer chromatography (TLC), reacted Finish, room temperature is cooled to, silica gel funnel is crossed, dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, suction filtration, after drying Obtain 77mmol compound 8, yield 77%.
Embodiment 9：The synthesis of compound 9
Under nitrogen protection, by two pyrazolo pyrene intermediate 101mmol, 4 bromobenzenes simultaneously [B, D] furans 220mmol, three (two BENZYLIDENE ACETONE) two palladium 5.0mmol, sodium tert-butoxide 405mmol, tri-butyl phosphine 20mmol are put in reaction vessel, are used in combination 500ml toluene dissolves, and 110 DEG C of back flow reaction 24h determine reaction end with thin-layer chromatography (TLC), and reaction is finished, and is cooled to room Temperature, crosses silica gel funnel, and dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 83mmolization after drying Compound 9, yield 82%.
Embodiment 10：The synthesis of compound 10
Under nitrogen protection, by two pyrazolo pyrene intermediate 102mmol, 2- (4- bromophenyl) benzo [d] thiazoles 222mmol, three (dibenzalacetone) two palladium 5.2mmol, sodium tert-butoxide 401mmol, tri-butyl phosphine 20mmol are put into reaction In container, and dissolved with 500ml toluene, 110 DEG C of back flow reaction 24h, reaction end is determined with thin-layer chromatography (TLC), reacted Finish, room temperature is cooled to, silica gel funnel is crossed, dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, suction filtration, after drying Obtain 89mmol compound 10, yield 88%.
Embodiment 11：The synthesis of compound 11
Under nitrogen protection, by two pyrazolo pyrene intermediate 100mmol, 2 (4- bromophenyl) -1,1- dimethyl -1H- indenes 223mmol, three (dibenzalacetone) two palladium 5.1mmol, sodium tert-butoxide 410mmol, tri-butyl phosphine 20.5mmol are put into instead Answer in container, and dissolved with 500ml toluene, 110 DEG C of back flow reaction 24h, reaction end is determined with thin-layer chromatography (TLC), reaction Finish, room temperature is cooled to, silica gel funnel is crossed, dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, suction filtration, dry After obtain 85mmol compound 11, yield 85%.
Embodiment 12：The synthesis of compound 12
Under nitrogen protection, by bromo- for two pyrazolo pyrene intermediate 100mmol, 9- 10- phenylanthracene 223mmol, three (two Asias Benzylacetone) two palladium 5.0mmol, sodium tert-butoxide 400mmol, tri-butyl phosphine 20mmol are put in reaction vessel, and use 500ml Toluene dissolves, and 110 DEG C of back flow reaction 24h determine reaction end with thin-layer chromatography (TLC), and reaction is finished, and is cooled to room temperature, mistake Silica gel funnel, dichloromethane are rinsed, and are spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 81mmol compound after drying 12, yield 81%.
Embodiment 13：The synthesis of compound 13
Under nitrogen protection, by two pyrazolo pyrene intermediate 102mmol, 4- bromine triphenylamine 225mmol, three (dibenzylidenes Acetone) two palladium 5.4mmol, sodium tert-butoxide 410mmol, tri-butyl phosphine 20.3mmol are put in reaction vessel, and use 500ml first Benzene dissolves, and 110 DEG C of back flow reaction 24h determine reaction end with thin-layer chromatography (TLC), and reaction is finished, and is cooled to room temperature, crosses silicon Glue funnel, dichloromethane are rinsed, and are spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 82mmol compound 13 after drying, Yield 82%.
Embodiment 14：The synthesis of compound 14
Under nitrogen protection, by two pyrazolo pyrene intermediate 103mmol, 2- bromoquinoline 225mmol, three (dibenzylidenes third Ketone) two palladium 5.1mmol, sodium tert-butoxide 405mmol, tri-butyl phosphine 20mmol be put in reaction vessel, and molten with 500ml toluene Solution, 110 DEG C of back flow reaction 24h, reaction end is determined with thin-layer chromatography (TLC), reaction is finished, and is cooled to room temperature, crosses silica gel leakage Bucket, dichloromethane are rinsed, and are spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 87mmol compound 14, yield after drying 84%.
Embodiment 15：The synthesis of compound 15
Under nitrogen protection, by two pyrazolo pyrene intermediate 100mmol, 2- bromine quinoxaline 223mmol, three (dibenzylidenes Acetone) two palladium 5.0mmol, sodium tert-butoxide 405mmol, tri-butyl phosphine 20.1mmol are put in reaction vessel, and use 500ml first Benzene dissolves, and 110 DEG C of back flow reaction 24h determine reaction end with thin-layer chromatography (TLC), and reaction is finished, and is cooled to room temperature, crosses silicon Glue funnel, dichloromethane are rinsed, and are spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 81mmol compound 15 after drying, Yield 81%.
Embodiment 16：The synthesis of compound 16
Under nitrogen protection, by two pyrazolo pyrene intermediate 101mmol, 4- (3- bromophenyl) dibenzothiophenes 220mmol, Three (dibenzalacetone) two palladium 5.2mmol), sodium tert-butoxide 405mmol, tri-butyl phosphine 20mmol are put in reaction vessel, And dissolved with 500ml toluene, 110 DEG C of back flow reaction 24h, reaction end is determined with thin-layer chromatography (TLC), reaction is finished, cooling To room temperature, silica gel funnel is crossed, dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, suction filtration, obtain after drying 79mmol compound 16, yield 78%.
Embodiment 17：The synthesis of compound 17
Under nitrogen protection, by two pyrazolo pyrene intermediate 103mmol, (4- bromophenyl) (phenyl) ketone 221mmol, three (dibenzalacetone) two palladium 5.1mmol, sodium tert-butoxide 400mmol, tri-butyl phosphine 20mmol are put in reaction vessel, are used in combination 500ml toluene dissolves, and 110 DEG C of back flow reaction 24h determine reaction end with thin-layer chromatography (TLC), and reaction is finished, and is cooled to room Temperature, crosses silica gel funnel, and dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 85mmolization after drying Compound 17, yield 83%.
Embodiment 18：The synthesis of compound 18
Under nitrogen protection, by bromo- for two pyrazolo pyrene intermediate 100mmol, 2- 9,9- dimethyl -9H- fluorenes 221mmol, Three (dibenzalacetone) two palladium 5.0mmol, sodium tert-butoxide 400mmol, tri-butyl phosphine 20.2mmol are put in reaction vessel, And dissolved with 500ml toluene, 110 DEG C of back flow reaction 24h, reaction end is determined with thin-layer chromatography (TLC), reaction is finished, cooling To room temperature, silica gel funnel is crossed, dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, suction filtration, obtain after drying 88mmol compound 18, yield 88%.
Embodiment 19：The synthesis of compound 19
Under nitrogen protection, by two pyrazolo pyrene intermediate 101mmol, 2- bromine pyrene 225mmol, three (dibenzalacetones) Two palladium 5.1mmol, sodium tert-butoxide 411mmol, tri-butyl phosphine 20mmol are put in reaction vessel, and are dissolved with 500ml toluene, 110 DEG C of back flow reaction 24h, determine reaction end with thin-layer chromatography (TLC), and reaction is finished, and are cooled to room temperature, cross silica gel funnel, Dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 80mmol compound 19, yield after drying 80%.
Embodiment 20：The synthesis of compound 20
Under nitrogen protection, by two pyrazolo pyrene intermediate 103mmol, 2- bromobenzenes simultaneously [9,10] phenanthrene 226mmol, three (two BENZYLIDENE ACETONE) two palladium 5.1mmol, sodium tert-butoxide 403mmol, tri-butyl phosphine 20.2mmol are put in reaction vessel, are used in combination 500ml toluene dissolves, and 110 DEG C of back flow reaction 24h determine reaction end with thin-layer chromatography (TLC), and reaction is finished, and is cooled to room Temperature, crosses silica gel funnel, and dichloromethane is rinsed, and is spin-dried for, dichloromethane/petroleum ether recrystallization, and suction filtration obtains 81mmolization after drying Compound 20, yield 79%.
By fast atom bombardment mass spectroscopy (FABMS) method, the elementary analysis of compound 1-20 is carried out.The results are shown in Table 1, Wherein MS/FAB (M+) is the molecular weight measured by FABMS：
Table 1
Comparative example
Using the compound of chemical formula a as light emitting host material, the compound of chemical formula b is used as dopant material, chemical formula c 2-TNATA (4,4,4- tri- (N- naphthyl)-N- the phenyl amino)-triphenylamine of expression) as hole-injecting material, chemical formula d table α-the NPD (N, N '-two (naphthyl)-N, N '-diphenylbenzidine) for showing, as hole mobile material, has made having for following structure Machine luminescent device：The compound of the compound+chemical formula b of ITO/2-TNATA (80nm)/α-NPD (30nm)/chemical formula a (30nm, wherein b content are 8%)/Al q3(30nm)/LiF(0.5nm)/Al(60nm).Wherein, Alq3It is 8-hydroxyquinoline aluminium.
By healthy and free from worry for Corning 15 Ω of society/cm2Ito glass substrate is cut into the chi of 50mm*50mm*0.7mm Very little.Subsequently in microwave, successively in acetone, isopropanol, cleaned 15 minutes in pure water respectively, cleaned 30 minutes in ultraviolet again. In the 2-TNATA of thereon vacuum evaporation 80nm thickness, hole injection layer is formed.Vacuum evaporation 30nm above hole injection layer α-the NPD of thickness, defines hole transporting layer.The change that the chemical formula a of vacuum evaporation 30nm thickness represents above hole transporting layer The compound doped rate 8% that compound and chemical formula b represent, defines luminescent layer.Vacuum evaporation 30nm thickness above luminescent layer Alq3, define electron supplying layer.Vacuum evaporation LiF 0.5nm (electron injection) and Al 60nm successively above electron supplying layer, Organic luminescent device is made.In the preparation embodiment of this comparative example and following organic luminescent device, public using DOV The EL evaporator of department's manufacture carries out vacuum evaporation.
The preparation embodiment of organic luminescent device：
Using the method in such as comparative example, the organic luminescent device with following structure is made, difference is As luminescent layer compound, the compound of chemical formula a is replaced to use in the compound of above-described embodiment 1-20 preparation one Kind：The compound of ITO/2-TNATA (80nm)/α-NPD (30nm)/type I compound+chemical formula b] (25nm, wherein b content is 8.0%)/Alq3(30nm) organic luminescent device of the structure of/LiF (0.5nm)/Al (60nm).
The luminescent properties of preparation embodiment sample 1-20 of comparative example's sample and organic luminescent device：
Under similarity condition, the sample of the preparation embodiment of the sample and organic luminescent device of comparative example is measured. Using 235 type source measuring unit of KEITHLEY Keithley, SpectrascanPR650 spectral scan colorimeter, to evaluate drive for measurement Dynamic voltage, luminosity, luminous efficiency, glow color.The results are shown in Table 2：
Table 2
According to table 2, above-mentioned sample shows glow color for blueness in 440-465nm wave-length coverage.Prepare real The sample of the sample and comparative example of applying example 1 to 20 compares, using organic of the organic layer of two pyrazolo pyrene analog derivatives Optical device can have the efficiency of lower driving voltage, higher brightness and Geng Gao.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.Right For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or Change.There is no need to be exhaustive to all of embodiment.And the obvious change thus extended out or Change among still in the protection domain of the invention.

Claims (5)

1. a kind of blue-light semiconductor material for containing two pyrazolo pyrenes, it is characterised in that the described blue light containing two pyrazolo pyrenes half Conductor material is the one kind in the compound shown in following structural formula：
2. the preparation method of the blue-light semiconductor material for containing two pyrazolo pyrenes according to claim 1, it is characterised in that bag Include following steps：
Step S1：Two pyrazolo pyrene intermediates, the bromide containing R group, catalyst, alkali is added in the reaction vessel after degassing And solvent；
Step S2：Rise high reaction temperature and flow back, fully react；
Step S3：Cooling, crosses silica gel funnel, washs, is spin-dried for, the blue-light semiconductor material being recrystallized to give containing two pyrazolo pyrenes；
The structural formula of the two pyrazolos pyrene intermediate is：
The bromide containing R group is：The bromo- 9H- carbazole of 9-, 2- bromonaphthalene, 3- bromine phenanthrene, the bromo- 4,7- phenanthroline of 2-, 3- bromine quinoline Bromo- 1- phenyl -1H- benzo [d] imidazoles of quinoline, 9- bromine anthracene, 3- bromine fluoranthene, 2-, the 4 bromobenzenes simultaneously bromo- 10- phenyl of [B, D] furans, 9- The bromo- 9,9- dimethyl -9H- fluorenes of anthracene, 4- bromine triphenylamine, 2- bromoquinoline, 2- bromine quinoxaline, 2-, 2- bromine pyrene or 2- bromobenzene simultaneously [9, 10] luxuriant and rich with fragrance.
3. the preparation method of the blue-light semiconductor material for containing two pyrazolo pyrenes according to claim 2, it is characterised in that step Two pyrazolo pyrene intermediates described in rapid S1 be by 1,6- dimethyl pyrene through nitrification, reduction, cyclization.
4. the preparation method of the blue-light semiconductor material for containing two pyrazolo pyrenes according to claim 3, it is characterised in that step Described in rapid S2, reaction temperature is 110 DEG C, and the time that is flowed back is 24h.
5. the organic luminescent device that a kind of blue-light semiconductor material containing two pyrazolo pyrenes by described in claim 1 is made, its Including first electrode, second electrode and be placed between the first electrode and the second electrode one or more organic Compound layer, it is characterised in that organic compound layer described at least one includes the blue-light semiconductor for containing two pyrazolo pyrenes Material.
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