CN103319531A - Organic semiconductor material, preparation method and electroluminescent device - Google Patents
Organic semiconductor material, preparation method and electroluminescent device Download PDFInfo
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- CN103319531A CN103319531A CN2012100722263A CN201210072226A CN103319531A CN 103319531 A CN103319531 A CN 103319531A CN 2012100722263 A CN2012100722263 A CN 2012100722263A CN 201210072226 A CN201210072226 A CN 201210072226A CN 103319531 A CN103319531 A CN 103319531A
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N C1CC=CCC1 Chemical compound C1CC=CCC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- RAFYVLOXJWISNV-UHFFFAOYSA-N COc(cc1)ccc1N(c(cc1)ccc1-c1cc(-c2ccccc2)c(-c2cccc3c2c-2ccc3)c-2c1-c1ccccc1)c(cc1)ccc1P(c1ccccc1)(c1ccccc1)=O Chemical compound COc(cc1)ccc1N(c(cc1)ccc1-c1cc(-c2ccccc2)c(-c2cccc3c2c-2ccc3)c-2c1-c1ccccc1)c(cc1)ccc1P(c1ccccc1)(c1ccccc1)=O RAFYVLOXJWISNV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides an organic semiconductor material, of which a chemical formula is shown by the following formula (I), wherein R is alkyl or alkoxy with 1-20 carbon atoms. The organic semiconductor material contains triphenylamine, fluoranthene and diphenyl phosphinyl groups, wherein the diphenyl phosphinyl groups have a good electronic transmission performance, and the organic semiconductor material can be used as a blue light main body material. The invention further provides a method for preparing the organic semiconductor material, and an electroluminescent device containing the organic semiconductor material.
Description
Technical field
The invention belongs to field of photovoltaic materials, be specifically related to a kind of organic semiconductor material, preparation method and electroluminescent device.
Background technology
1987, the Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in the organic electroluminescent research.They utilize vacuum evaporation technology higher and have an oxine aluminium (Alq of electron-transporting having the aromatic diamine of hole transport ability and fluorescence efficiency first
3) combined preparation gone out double-deck organic electroluminescence device.Device under the 10V driving voltage, transmitting green light, brightness is up to 1000cd/m
2, efficient reaches 1.5lm/W, and the life-span was above 1000 hours.This landmark work makes people see organic electroluminescent practicability and business-like rosy prospect.
The electro phosphorescent device that adopts Subjective and Objective to mix, in luminescence process, can utilize singlet and triplet excitons simultaneously, internal quantum efficiency can reach 100% in theory, and therefore the electro phosphorescent device that adopts this Subjective and Objective to mix becomes the main path that improves device efficiency.The selection of material of main part is most important, especially at present the blue light material of main part relatively lacks, material of main part should meet the following conditions: the one, and the emmission spectrum of main body and the absorption spectrum of object have bigger overlapping, and after main body was excited like this, energy can successfully be transferred to guest molecule; The 2nd, the quenching effect of the exciton energy of main object is little, and namely the triplet energy state of main body will be higher than object; The 3rd, material of main part should have good carrier mobility character; The 4th, should have good consistency between the subject and object, prevent from being separated and cause concentration quenching.
Triphenylamine and derivative thereof have higher hole mobility and higher triplet, solvability and amorphous film-forming preferably, and therefore stronger fluorescence property and light stability are widely used in photoelectric material and hole mobile material.Yet the electronic transmission performance of triphenylamine and fluoranthene is all bad.
Summary of the invention
For addressing the above problem, the invention provides a kind of organic semiconductor material, this organic semiconductor material contains triphenylamine, fluoranthene and diphenyl phosphine oxygen base, wherein diphenyl phosphine oxygen base has the good electron transmission performance, and organic semiconductor material of the present invention provides new selectable kind for the blue light material of main part.The present invention also provides the preparation method of this organic semiconductor material, and the electroluminescent device that comprises this organic semiconductor material.
On the one hand, the invention provides a kind of organic semiconductor material, the chemical formula of described organic semiconductor material is suc as formula shown in (I):
R is C
1～C
20Alkyl or alkoxyl group.
Among the present invention, organic semiconductor material contains triphenylamine, fluoranthene and diphenyl phosphine oxygen base, rigidity substituting group fluoranthene makes material have excellent hole transport performance, the fluoranthene group has excellent fluorescence quantum efficiency, and owing to introduced trianilino group in the structure, triphenylamine has high triplet and hole transport ability, improved the solvability of material, improved the film-forming properties of material, diphenyl phosphine oxygen base has good electronic transmission performance in addition, this kind material can be used as the material of main part of high efficiency phosphorescent electroluminescent device, is conducive to obtain high efficiency electroluminous device.
Second aspect the invention provides a kind of preparation method of organic semiconductor material, comprises the steps:
Compound D is provided:
Under inert atmosphere, Compound D is dissolved in the organic solvent, be cooled to-78 ℃, in the organic solvent that is dissolved with Compound D, add n-Butyl Lithium, the mol ratio of described Compound D and described n-Butyl Lithium is 1: 1.1～1.2, add diphenyl phosphine chloride after stirring 1～5h, the mol ratio of described Compound D and described diphenyl phosphine chloride is 1: 1.1～1.2, temperature of reaction is risen to stirring at room reaction 3～12h, after adding water termination reaction, the extraction organic layer, adopt silica gel column chromatography to separate purification and obtain solid product, be dissolved into described solid product in methylene dichloride or the chloroform and added hydrogen peroxide oxidation 12～24 hours, make organic semiconductor material, the chemical formula of described organic semiconductor material is suc as formula shown in (I):
Wherein R is C
1～C
20Alkyl or alkoxyl group.
Preferably, silica gel column chromatography separates purification step and adopts sherwood oil to carry out silica gel column chromatography with methylene dichloride as leacheate to separate.
Preferably, this preparation method further comprises post-processing step, described post-processing step is that saturated aqueous common salt and distilled water wash are adopted in organic semiconductor material dissolving back, revolve steam adopt behind the solvent ethyl acetate and methyl alcohol as developping agent through the silicagel column separation and purification.
Preferably, organic solvent is selected from tetrahydrofuran (THF), ether, isopropyl ether, ethyl-butyl ether or glycol dimethyl ether.
Preferably, Compound D:
The preparation method as follows:
Compd B is provided:
R is C
1～C
20Alkyl or alkoxyl group,
And Compound C:
With compd B in tetrahydrofuran (THF) and methanol mixed solvent, drip basic solution, reaction mixture stirs at ambient temperature, then washing, dry then, revolve and desolventize, then the solid matter that obtains is dissolved in the organic solvent, vacuumize the feeding rare gas element, and adding Compound C, the mol ratio of described compd B and Compound C is 1: 1～1: 1.1, and reacting by heating 24 hours finishes after the reaction reaction mixture purifying to be obtained Compound D.More preferably, the step that purifying makes Compound D comprises adding ethanol after-filtration precipitation in the reaction mixture, uses washing with alcohol then, adopts column chromatography to separate after the vacuum-drying.More preferably, the solid matter that obtains is dissolved in organic solvent p-Xylol, o-Xylol or the m-xylene.
More preferably, described compd B:
The preparation method as follows:
Compd A is provided:
R is C
1～C
20Alkyl or alkoxyl group, under inert atmosphere, in being housed, the reaction vessel of compd A adds organic solvent, cool to and be-78 ℃, drip n-Butyl Lithium then, the mol ratio of described n-Butyl Lithium and compd A is 1～1.2: 1, n-Butyl Lithium adds trimethylsilyl acetylene after dropwising the back stirring reaction, the mol ratio of described trimethylsilyl acetylene and compd A is 1～1.2: 1 stirring reaction 1 hour, is warming up to normal temperature, will obtain compd B behind the reaction soln purifying.Wherein preferably, the step that purifying makes compd B comprises the reaction mixture chloroform extraction, and water, bromine and magnesium sulfide drying successively adopt normal hexane developping agent column chromatography to separate at last then.And wherein preferably, the organic solvent that adds in the reaction vessel of compd A is housed is selected from tetrahydrofuran (THF), ether, isopropyl ether, ethyl-butyl ether or glycol dimethyl ether.
The third aspect the invention provides a kind of electroluminescent device, comprising:
Comprise the substrate with anode, luminescent layer and the cathode layer that stack gradually, the material of described luminescent layer is suc as formula shown in (I):
R is C
1～C
20Alkyl or alkoxyl group.
The invention provides a kind of organic semiconductor material, preparation method and electroluminescent device, have following beneficial effect: (1) organic semiconductor material of the present invention has higher hole mobility and high triplet because containing fluoranthene and trianilino group in the structure, simultaneously has electron-transporting preferably because containing the hexichol phosphorus-oxygen groups in the structure, therefore organic semiconductor material of the present invention can be used as the blue light material of main part in the phosphorescence electroluminescent device, is conducive to obtain high efficiency electroluminous device; (2) have good solubility, material easily is dissolved in the organic solvent commonly used such as tetrahydrofuran (THF), methylene dichloride, toluene, chloroform, is applicable in the organic electroluminescence device Application for Field; (3) electroluminescent device luminous efficiency height.
Description of drawings
Fig. 1 is to be the structural representation of the organic electroluminescence device that makes of material of main part with the organic semiconductor material that makes among the embodiment 1;
Fig. 2 is the luminescent spectrum figure of the organic electroluminescence device that makes among the embodiment 1;
Fig. 3 is the luminous efficiency-current density graphic representation of the organic electroluminescence device that makes among the embodiment 1.
Embodiment
The following stated is preferred implementation of the present invention.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also make some improvement and adjustment, these improvement and adjustment also are considered as in protection scope of the present invention.
Embodiment 1:
A kind of organic semiconductor material: 4-methoxyl group-4 '-(7,10-phenylbenzene fluoranthene base)-4 " diphenyl phosphine oxygen base triphenylamine (called after DPFPOMOTPA among the present invention), shown in (Ia):
Its preparation method comprises the steps:
(1) be prepared as follows the compd B that structural formula is represented: 4-trimethylsilyl acetylene-4 '-methoxyl group-4 " the bromine triphenylamine,
B：
Be connected with in the there-necked flask of nitrogen to one, add compd A: 4-methoxyl group-4 ', 4 " the dibromo triphenylamine (6.49g; 15mmol); vacuumize logical nitrogen three times; squeeze into tetrahydrofuran (THF) (THF) solvent with syringe then, the ethanol bath cooling is-78 ℃, slowly drip then n-Butyl Lithium n-BuLi (2.5M in hexane) (6mL; 15mmol); dropwise back stirring reaction half an hour, add then trimethylsilyl acetylene (1.76g, 18mmol), stirring reaction 1h, be warming up to normal temperature, chloroform extraction mixed solution, water, bromine and MgSO successively then
4Drying adopts normal hexane developping agent column chromatography to separate then, obtains product B (6.08g, productive rate 90%).
MS：m/z?451.
1H?NMR(400MHz，CDCl
3，ppm)δ：7.38(d，6H)，7.05(d，6H)，4.02(s，3H)，0.21(s，18H)。
Step (1) reaction formula is as follows:
(2) be prepared as follows the Compound D that structural formula is represented: 4-methoxyl group-4 '-(7,10-phenylbenzene fluoranthene base)-4 " the bromine triphenylamine,
In the tetrahydrofuran (THF) and methanol mixed solvent of compd B, drip NaOH aqueous solution 5N, reaction mixture is at stirring at room 1h, add ethyl acetate then, water, bromine washing, anhydrous sodium sulfate drying, revolve and desolventize, obtain product 4-ethynyl-4 '-methoxyl group-4 " bromo triphenylamine
Product 4-ethynyl-4 '-methoxyl group-4 " the bromo triphenylamine:
This product 4-ethynyl-4 '-methoxyl group-4 " add Compound C in the bromo triphenylamine: 7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone (5.34g, 15mmol),
C：
Logical argon gas adds the organic solvent p-Xylol, and 160 ℃ of heating 24h after the question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, and washing with alcohol, vacuum-drying, column chromatography is separated, and obtains product D (8.56g, productive rate 81%),
D：
MS：m/z?705.
1H?NMR(CD
2Cl
2，400MHz，ppm)δ：7.98-7.88(m，4H)，7.81-7.72(m，3H)，7.58-7.28(m，12H)，7.15(m，9H)，6.89(d，1H)，4.01(s，3H)。
Step (2) reaction formula is as follows:
(3) preparation suc as formula the compound 4-methoxyl group-4 shown in (Ia) '-(7,10-phenylbenzene fluoranthene base)-4 " diphenyl phosphine oxygen base triphenylamine (called after DPFPOMOTPA among the present invention):
Anaerobic is anhydrous to be reached under-78 ℃ of ethanol bath, with n-Butyl Lithium (2.5M in hexane) (7.2mL, 18mmol) be added drop-wise in the tetrahydrofuran solution of Compound D, behind the stirring reaction 3h with diphenyl phosphine chloride (3.35mL, 18mmol) add wherein, obtain transparent pale yellow solution, be warming up to stirring reaction 12h after the room temperature naturally.Ethyl acetate extraction is adopted in water (100mL) cancellation reaction, concentrates organic layer, and crude product adopts sherwood oil/methylene dichloride to separate to purify through silica gel column chromatography as leacheate and obtains white solid product.And then with methylene dichloride (70mL) dissolving, adding 30% hydrogen peroxide (8mL), stirring reaction 12h under the room temperature separates organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve the steaming solvent, adopt ethyl acetate/methanol to separate to purify through silicagel column as developping agent and obtain the compound shown in the white solid formula (Ia) (7.57g, productive rate 61%).
Step (3) reaction formula is as follows:
MS：m/z?827.
1H?NMR(CD
2Cl
2，400MHz，ppm)δ：7.98-7.88(m，4H)，7.81-7.72(m，3H)，7.58-7.28(m，12H)，7.21-7.15(m，19H)，6.89(d，1H)，4.01(s，3H)。
A kind of electroluminescent device comprises:
Comprise the substrate with anode, luminescent layer and the cathode layer that stack gradually, the material of described luminescent layer is compound 4-methoxyl group-4 '-(7,10-phenylbenzene fluoranthene base)-4 " diphenyl phosphine oxygen base triphenylamine (called after DPFPOMOTPA among the present invention), shown in (Ia):
Fig. 1 be the 4-methoxyl group-4 of using the embodiment of the invention 1 preparation '-" diphenyl phosphine oxygen base triphenyl amine compound (Ia) is as the electroluminescent device structure iron of the material of luminescent layer for (7,10-phenylbenzene fluoranthene base)-4.As shown in Figure 1, this organic electroluminescence device is straticulate structure, glass substrate 1, transparent anode 2, hole transmission layer 3, luminescent layer 4, hole blocking layer 5, electron transfer layer 6, buffer layer 7 and negative electrode 8, its structure is: and ITO/m-MTDATA:F4-TCNQ/DPFPOMOTPA:FIrpic (10wt%)/Bphen/Bphen:Cs/Mg: Ag (10: 1, wt%)/Ag.
Electroluminescent device in the present embodiment adopts the method preparation of vacuum evaporation, evaporation anode 2 on glass substrate 1 at first, material is chosen as ITO, it is tin indium oxide, with ito glass spin coating photoresist material, exposure, development, chloroazotic acid etching, be etched into needed pattern and size, then that etching is good conductive glass cleans, use each ultrasonic cleaning 15min such as pure water, acetone, ethanol successively, clean up the back it is carried out oxygen plasma treatment, the oxygen plasma treatment time is 15min, and power is 35W, improves the surperficial work content of conductive glass with this.Then ito glass is put into the organic vacuum cavity, evaporation p-doping hole transmission layer m-MTDATA:F4-TCNQ 40nm, luminescent layer DPFPOMOTPA:FIrpic (10wt%) 30nm, hole blocking layer Bphen10nm, n-doping electron transfer layer Bphen:Cs 40nm successively, then substrate is moved into metallic cavity, continue evaporation negative electrode magnesium silver alloys Mg: Ag (10: 1, wt%) 150nm, the Ag of last evaporation one deck 10nm obtains needed efficient blue light electroluminescent device at last.It is m-MTDATA:F4-TCNQ that above-mentioned hole transmission layer 3 is selected materials, wherein m-MTDATA be 4,4 ', 4 " three (3-aminomethyl phenyl aniline) triphenylamine, F4-TCNQ is tetrafluoro four cyano para benzoquinone bismethane; It is DPFPOMOTPA:FIrpic (10wt%) that luminescent layer 4 is selected material, wherein DPFPOMOTPA be embodiment 1 preparation 4-methoxyl group-4 '-" diphenyl phosphine oxygen base triphenyl amine compound (Ia), FIrpic be pairs (4; 6-difluorophenyl pyridine-N, C to (7,10-phenylbenzene fluoranthene base)-4
2') the pyridine formyl closes iridium; It is Bphen that hole blocking layer 5 is selected materials, namely 4, and 7-phenylbenzene-1,10-phenanthroline; It is Bphen:Cs that electron transfer layer 6 is selected material; Buffer layer 7 materials are chosen as Mg: and Ag (10: 1, wt%); Last evaporation negative electrode 8 materials are chosen as silver.
Fig. 2 is the luminescent spectrum figure of the organic electroluminescence device that makes among the embodiment 1.As can be seen from Figure 2, maximum emission peak is 470nm, is the emission peak of object FIrpic, does not have the emission peak of main body, illustrate that the energy from the main body to the object has taken place to be shifted, and illustrates that the triplet of material of main part is higher than the triplet 2.7eV of object FIrpic.
Fig. 3 is the luminous efficiency-current density graphic representation of the organic electroluminescence device that makes among the embodiment 1.As can be seen from Figure 3, the maximum lumen efficient of device is 21.04lm/W, and corresponding current density is 12.44mA/cm
2, illustrating that the current carrier composite efficiency of device is higher, the carrier transport efficient that further illustrates material of main part is higher.
Embodiment 2:
A kind of organic semiconductor material: the 4-tertiary butyl-4 '-(7,10-phenylbenzene fluoranthene base)-4 " diphenyl phosphine oxygen base triphenylamine (called after DPFPOtBTPA among the present invention), shown in (I b):
Its preparation method comprises the steps:
(1) be prepared as follows the compd B that structural formula is represented: 4-trimethylsilyl acetylene-4 '-tertiary butyl-4 " the bromine triphenylamine,
B：
Be connected with in the there-necked flask of argon gas to one, add compd A: the 4-tertiary butyl-4 ', 4 " the dibromo triphenylamine (6.88g; 15mmol); vacuumize logical argon gas three times; squeeze into ether solvent with syringe then, the ethanol bath cooling is-78 ℃, slowly drip then n-Butyl Lithium n-BuLi (2.5M in hexane) (7.2mL; 18mmol); dropwise back stirring reaction half an hour, add then trimethylsilyl acetylene (1.76g, 18mmol), stirring reaction 1h, be warming up to normal temperature, chloroform extraction mixed solution, water, bromine and MgSO successively then
4Drying adopts normal hexane developping agent column chromatography to separate then, obtains product B (6.51g, productive rate 91%).
MS：m/z?477.
1H?NMR(400MHz，CDCl
3，ppm)δ：7.38(d，6H)，7.05(d，6H)，1.38(s，9H)，0.21(s，18H)。
Step (1) reaction formula is as follows:
(2) be prepared as follows the Compound D that structural formula is represented: the 4-tertiary butyl-4 '-(7,10-phenylbenzene fluoranthene base)-4 " the bromine triphenylamine,
In the tetrahydrofuran (THF) and methanol mixed solvent of compd B, drip NaOH aqueous solution 5N, reaction mixture is at stirring at room 1h, add ethyl acetate then, water, bromine washing, anhydrous sodium sulfate drying, revolve and desolventize, obtain product 4-ethynyl-4 '-tertiary butyl-4 " bromo triphenylamine
Product 4-ethynyl-4 '-tertiary butyl-4 " the bromo triphenylamine:
Get above-mentioned product 4-ethynyl-4 '-tertiary butyl-4 " the bromo triphenylamine adds Compound C: 7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone (5.87g, 16.5mmol),
C：
Logical argon gas adds the organic solvent o-Xylol, and 170 ℃ of heating 24h after the question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, and washing with alcohol, vacuum-drying, column chromatography is separated, and obtains product D (8.77g, productive rate 80%),
D：
MS：m/z?731.
1H?NMR(CD
2Cl
2，400MHz，ppm)δ：7.98-7.88(m，4H)，7.81-7.72(m，3H)，7.58-7.28(m，12H)，7.15(m，9H)，6.89(d，1H)，1.41(s，9H)。
Step (2) reaction formula is as follows:
(3) preparation suc as formula the compound 4-tertiary butyl-4 shown in (Ib) '-(7,10-phenylbenzene fluoranthene base)-4 " diphenyl phosphine oxygen base triphenylamine (called after DPFPOtBTPA among the present invention):
Anaerobic is anhydrous to be reached under-78 ℃ of ethanol bath, with n-Butyl Lithium (2.5M in hexane) (6.6mL, 16.5mmol) be added drop-wise to the Compound D 4-tertiary butyl-4 '-(7,10-phenylbenzene fluoranthene base)-4 " in the ether of bromine triphenylamine; (3.07mL; 16.5mmol) add wherein, obtain transparent pale yellow solution is warming up to stirring reaction 3h after the room temperature naturally with diphenyl phosphine chloride behind the stirring reaction 5h.Ethyl acetate extraction is adopted in water (100mL) cancellation reaction, concentrates organic layer, and crude product adopts sherwood oil/methylene dichloride to separate to purify through silica gel column chromatography as leacheate and obtains white solid product.And then with chloroform (70mL) dissolving, adding 30% hydrogen peroxide (8mL), stirring reaction 24h under the room temperature separates organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve the steaming solvent, adopt ethyl acetate/methanol to separate to purify through silicagel column as developping agent and obtain the compound shown in the white solid formula (Ib) (7.94g, productive rate 62%).
Step (3) reaction formula is as follows:
MS：m/z?853.
1H?NMR(CD
2Cl
2，400MHz，ppm)δ：7.98-7.88(m，4H)，7.81-7.72(m，3H)，7.58-7.28(m，12H)，7.21-7.15(m，19H)，6.89(d，1H)，1.42(s，9H)。
Embodiment 3:
A kind of organic semiconductor material: 4-hexyloxy-4 '-(7,10-phenylbenzene fluoranthene base)-4 " diphenyl phosphine oxygen base triphenylamine (called after DPFPOHOTPA among the present invention), shown in (Ic):
Its preparation method comprises the steps:
(1) be prepared as follows the compd B that structural formula is represented: 4-trimethylsilyl acetylene-4 '-hexyloxy-4 " the bromine triphenylamine,
B：
Be connected with in the there-necked flask of nitrogen to one, add compd A: 4-hexyloxy-4 ', 4 " the dibromo triphenylamine (7.55g; 15mmol); vacuumize logical nitrogen three times; squeeze into the isopropyl ether solvent with syringe then, the ethanol bath cooling is-78 ℃, slowly drip then n-Butyl Lithium n-BuLi (2.5M in hexane) (7.2mL; 18mmol); dropwise back stirring reaction half an hour, add then trimethylsilyl acetylene (1.76g, 18mmol), stirring reaction 1h, be warming up to normal temperature, chloroform extraction mixed solution, water, bromine and MgSO successively then
4Drying adopts normal hexane developping agent column chromatography to separate then, obtains product B (7.26g, productive rate 93%).
MS：m/z?521.
1H?NMR(400MHz，CDCl
3，ppm)δ：7.38(d，6H)，7.05(d，6H)，4.02(t，2H)，1.32-1.78(m，11H)，0.21(s，18H)。
Step (1) reaction formula is as follows:
(2) be prepared as follows the Compound D that structural formula is represented: 4-hexyloxy-4 '-(7,10-phenylbenzene fluoranthene base)-4 " the bromine triphenylamine,
In the tetrahydrofuran (THF) and methanol mixed solvent of compd B, drip NaOH aqueous solution 5N, reaction mixture is at stirring at room 1h, add ethyl acetate then, water, bromine washing, anhydrous sodium sulfate drying, revolve and desolventize, obtain product 4-ethynyl-4 '-hexyloxy-4 " bromo triphenylamine
Product 4-ethynyl-4 '-hexyloxy-4 " the bromo triphenylamine:
Get above-mentioned product 4-ethynyl-4 '-hexyloxy-4 " the bromo triphenylamine adds Compound C then: 7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone (5.61g, 15.75mmol),
C：
Logical argon gas adds the organic solvent p-Xylol, and 165 ℃ of heating 24h after the question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, and washing with alcohol, vacuum-drying, column chromatography is separated, and obtains product D (9.41g, productive rate 81%),
D：
MS：m/z?775.
1H?NMR(CD
2Cl
2，400MHz，ppm)δ：7.98-7.88(m，4H)，7.81-7.72(m，3H)，7.58-7.28(m，12H)，7.15(m，9H)，6.89(d，1H)，4.01(t，2H)，1.32-1.78(m，11H)。
Step (2) reaction formula is as follows:
(3) preparation suc as formula the compound 4-hexyloxy-4 shown in (Ic) '-(7,10-phenylbenzene fluoranthene base)-4 " diphenyl phosphine oxygen base triphenylamine (called after DPFPOHOTPA among the present invention):
Anaerobic is anhydrous to be reached under-78 ℃ of ethanol bath, with n-Butyl Lithium (2.5M in hexane) (7.2mL, 18mmol) be added drop-wise to Compound D: 4-hexyloxy-4 '-(7,10-phenylbenzene fluoranthene base)-4 " in the ethylene glycol dimethyl ether solution of bromine triphenylamine; (3.35mL; 18mmol) add wherein, obtain transparent pale yellow solution is warming up to stirring reaction 8h after the room temperature naturally with diphenyl phosphine chloride behind the stirring reaction 1h.Ethyl acetate extraction is adopted in water (100mL) cancellation reaction, concentrates organic layer, and crude product adopts sherwood oil/methylene dichloride to separate to purify through silica gel column chromatography as leacheate and obtains white solid product.And then with methylene dichloride (70mL) dissolving, adding 30% hydrogen peroxide (8mL), stirring reaction 18h under the room temperature separates organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve the steaming solvent, adopt ethyl acetate/methanol to separate to purify through silicagel column as developping agent and obtain the compound shown in the white solid formula (Ic) (8.61g, productive rate 64%).
Step (3) reaction formula is as follows:
MS：m/z?897.
1H?NMR(CD
2Cl
2，400MHz，ppm)δ：7.98-7.88(m，4H)，7.81-7.72(m，3H)，7.58-7.28(m，12H)，7.21-7.15(m，19H)，6.89(d，1H)，4.01(t，2H)，1.32-1.78(m，11H)。
Embodiment 4:
A kind of organic semiconductor material: 4-eicosyl-4 '-(7,10-phenylbenzene fluoranthene base)-4 " diphenyl phosphine oxygen base triphenylamine (called after DPFPOITPA among the present invention), shown in (Id):
Its preparation method comprises the steps:
(1) be prepared as follows the compd B that structural formula is represented: 4-trimethylsilyl acetylene-4 '-eicosyl-4 " the bromine triphenylamine),
B：
Be connected with in the there-necked flask of nitrogen to one, add compd A: 4-eicosyl-4 ', 4 " the dibromo triphenylamine (10.25g; 15mmol); vacuumize logical nitrogen three times; squeeze into the ethyl-butyl ether solvents with syringe then, the ethanol bath cooling is-78 ℃, slowly drip then n-Butyl Lithium n-BuLi (2.5M in hexane) (6mL; 15mmol); dropwise back stirring reaction half an hour, add then trimethylsilyl acetylene (1.76g, 18mmol), stirring reaction 1h, be warming up to normal temperature, chloroform extraction mixed solution, water, bromine and MgSO successively then
4Drying adopts normal hexane developping agent column chromatography to separate then, obtains product B (9.67g, productive rate 92%).
MS：m/z?701.
1H?NMR(400MHz，CDCl
3，ppm)δ：7.38(d，6H)，7.05(d，6H)，2.02(t，2H)，1.27-1.79(m，39H)，0.21(s，18H)。
Step (1) reaction formula is as follows:
(2) be prepared as follows the Compound D that structural formula is represented: 4-eicosyl-4 '-(7,10-phenylbenzene fluoranthene base)-4 " the bromine triphenylamine,
In the tetrahydrofuran (THF) and methanol mixed solvent of compd B, drip NaOH aqueous solution 5N, reaction mixture is at stirring at room 1h, add ethyl acetate then, water, bromine washing, anhydrous sodium sulfate drying, revolve and desolventize, obtain product 4-ethynyl-4 '-eicosyl-4 " bromo triphenylamine
Product 4-ethynyl-4 '-eicosyl-4 " the bromo triphenylamine:
Get above-mentioned product 4-ethynyl-4 '-eicosyl-4 " the bromo triphenylamine adds Compound C then: 7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone (5.34g, 15mmol),
C：
Logical argon gas adds the organic solvent p-Xylol, and 160 ℃ of heating 24h after the question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, and washing with alcohol, vacuum-drying, column chromatography is separated, and obtains product D (11.89g, productive rate 82%),
D：
MS：m/z?955.
1H?NMR(CD
2Cl
2，400MHz，ppm)δ：7.98-7.88(m，4H)，7.81-7.72(m，3H)，7.58-7.28(m，12H)，7.15(m，9H)，6.89(d，1H)，2.01(t，2H)，1.27-1.76(m，39H)。
Step (2) reaction formula is as follows:
(3) preparation suc as formula the compound 4-eicosyl-4 shown in (Id) '-(7,10-phenylbenzene fluoranthene base)-4 " diphenyl phosphine oxygen base triphenylamine (called after DPFPOITPA among the present invention):
Anaerobic is anhydrous to be reached under-78 ℃ of ethanol bath, with n-Butyl Lithium (2.5M in hexane) (7.2mL, 18mmol) be added drop-wise to Compound D: 4-eicosyl-4 '-(7,10-phenylbenzene fluoranthene base)-4 " in the ethyl-butyl ether of bromine triphenylamine; (3.35mL; 18mmol) add wherein, obtain transparent pale yellow solution is warming up to stirring reaction 10h after the room temperature naturally with diphenyl phosphine chloride behind the stirring reaction 4h.Ethyl acetate extraction is adopted in water (100mL) cancellation reaction, concentrates organic layer, and crude product adopts sherwood oil/methylene dichloride to separate to purify through silica gel column chromatography as leacheate and obtains white solid product.And then with methylene dichloride (70mL) dissolving, adding 30% hydrogen peroxide (8mL), stirring reaction 16h under the room temperature separates organic layer, respectively with saturated aqueous common salt and distillation washing.Revolve the steaming solvent, adopt ethyl acetate/methanol to separate to purify through silicagel column as developping agent and obtain white solid suc as formula (9.69g, productive rate 60%) shown in (Id).
Step (3) reaction formula is as follows:
MS：m/z?1077.
1H?NMR(CD
2Cl
2，400MHz，ppm)δ：7.98-7.88(m，4H)，7.81-7.72(m，3H)，7.58-7.28(m，12H)，7.21-7.15(m，19H)，6.89(d，1H)，2.01(t，2H)，1.27-1.76(m，39H)。
Claims (10)
1. an organic semiconductor material is characterized in that, the chemical formula of described organic semiconductor material is suc as formula shown in (I):
R is C
1～C
20Alkyl or alkoxyl group.
2. the preparation method of an organic semiconductor material is characterized in that, comprises the steps:
Compound D is provided:
Under inert atmosphere, Compound D is dissolved in the organic solvent, be cooled to-78 ℃, in the organic solvent that is dissolved with Compound D, add n-Butyl Lithium, the mol ratio of described Compound D and described n-Butyl Lithium is 1: 1.1～1.2, add diphenyl phosphine chloride after stirring 1～5h, the mol ratio of described Compound D and described diphenyl phosphine chloride is 1: 1.1～1.2, temperature of reaction is risen to stirring at room reaction 3～12h, after adding water termination reaction, the extraction organic layer, adopt silica gel column chromatography to separate purification and obtain solid product, be dissolved into described solid product in methylene dichloride or the chloroform and added hydrogen peroxide oxidation 12～24 hours, make organic semiconductor material, the chemical formula of described organic semiconductor material is suc as formula shown in (I):
Wherein R is C
1～C
20Alkyl or alkoxyl group.
3. preparation method as claimed in claim 2 is characterized in that, described silica gel column chromatography separation purification step employing sherwood oil carries out silica gel column chromatography with methylene dichloride as leacheate to be separated.
4. preparation method as claimed in claim 2, it is characterized in that, described preparation method further comprises post-processing step, described post-processing step is that saturated aqueous common salt and distilled water wash are adopted in organic semiconductor material dissolving back, revolve steam adopt behind the solvent ethyl acetate and methyl alcohol as developping agent through the silicagel column separation and purification.
5. preparation method as claimed in claim 2 is characterized in that, described organic solvent is selected from tetrahydrofuran (THF), ether, isopropyl ether, ethyl-butyl ether or glycol dimethyl ether.
6. preparation method as claimed in claim 2 is characterized in that, described Compound D:
The preparation method as follows:
Compd B is provided:
R is C
1～C
20Alkyl or alkoxyl group,
And Compound C:
With compd B in tetrahydrofuran (THF) and methanol mixed solvent, drip basic solution, reaction mixture stirs at ambient temperature, then washing, dry then, revolve and desolventize, then the solid matter that obtains is dissolved in the organic solvent, vacuumize the feeding rare gas element, and adding Compound C, the mol ratio of described compd B and Compound C is 1: 1～1.1,160 ℃～170 ℃ reacting by heating 24 hours, finishes after the reaction reaction mixture purifying to be obtained Compound D.
7. preparation method as claimed in claim 6 is characterized in that, the step that described purifying makes Compound D comprises adding ethanol after-filtration precipitation in the reaction mixture, uses washing with alcohol then, adopts column chromatography to separate after the vacuum-drying.
8. preparation method as claimed in claim 6 is characterized in that, described compd B:
The preparation method as follows: compd A is provided:
R is C
1～C
20Alkyl or alkoxyl group, under inert atmosphere, in being housed, the reaction vessel of described compd A adds organic solvent, cool to-78 ℃, drip n-Butyl Lithium then, the mol ratio of described n-Butyl Lithium and described compd A is 1～1.2: 1, described n-Butyl Lithium adds trimethylsilyl acetylene after dropwising the back stirring reaction, the mol ratio of described trimethylsilyl acetylene and described compd A is 1～1.2: 1 stirring reaction 1 hour, is warming up to normal temperature, will obtain compd B behind the reaction soln purifying.
9. preparation method as claimed in claim 8 is characterized in that, the step that described purifying makes compd B comprises the reaction mixture chloroform extraction, and water, bromine and magnesium sulfide drying successively adopt normal hexane developping agent column chromatography to separate at last then.
10. an electroluminescent device is characterized in that, comprising:
Comprise the substrate with anode, luminescent layer and the cathode layer that stack gradually, the material of described luminescent layer is suc as formula the organic semiconductor material shown in (I):
R is C
1～C
20Alkyl or alkoxyl group.
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| CN101432251A (en) * | 2006-04-27 | 2009-05-13 | 佳能株式会社 | 4-arylfluorene compound and organic light-emitting device using same |
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| CN101432251A (en) * | 2006-04-27 | 2009-05-13 | 佳能株式会社 | 4-arylfluorene compound and organic light-emitting device using same |
| CN101747372A (en) * | 2010-01-21 | 2010-06-23 | 中国科学院长春应用化学研究所 | Arylamine compound, organic electroluminescent device containing arylamine compound and preparation method thereof |
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