CN103159584B - Bi-fluoranthene-containing organic semiconductor material, its preparation method and application - Google Patents
Bi-fluoranthene-containing organic semiconductor material, its preparation method and application Download PDFInfo
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Abstract
Belonging to the field of organic semiconductor materials, the invention discloses a bi-fluoranthene-containing organic semiconductor material, its preparation method and application. The bi-fluoranthene-containing organic semiconductor material has a chemical structural formula shown in the description, wherein R is linear chain alkyl of C1-C12. The fluorine-containing bi-fluoranthene organic semiconductor material provided in the invention has good solubility, and is easily dissolved in tetrahydrofuran, dichloromethane, toluene, chloroform and other common organic solvents, thus being easy to process. Because of the fluoranthene groups existing in the structure, the luminescent material has high hole mobility, and at the same time, the compound can emit pure blue light. Therefore, the material can form efficient and stable blue electroluminescent devices.
Description
Technical field
The present invention relates to organic semiconductor material field, particularly relate to a kind of containing two fluoranthene organic semiconductor material and its preparation method and application.
Background technology
1987, Tang and VanSlyke of Eastman Kodak company of the U.S. reported the breakthrough in organic electroluminescent research.They utilize vacuum evaporation technology higher to the aromatic diamine and fluorescence efficiency with hole transport ability and have the oxine aluminium (Alq of electron-transporting first
3) combine and prepared double-deck organic electroluminescence device.Device is under 10V driving voltage, and transmitting green light, brightness is up to 1000cd/m
2, efficiency reaches 1.5lm/W, and the life-span was more than 1000 hours.This landmark work makes people see the practical and business-like rosy prospect of organic electroluminescent.
In recent years, there is efficient, energy-conservation Organic Light Emitting Diode and cause people's interest widely in display field and lighting field.Realize the application purpose such as total colouring and illumination, in three primary colours, blue light is absolutely necessary.Meanwhile, because blue light energy is the highest, as long as there is good material just can obtain green glow and ruddiness by multiple method.Therefore the luminescent properties improving blue light to realize organic electroluminescent total colouring and solid luminescence significant.But because the energy of blue light is high, efficiency and stability do not have green glow and red light material good, simultaneously the carrier transmission performance of material neither be fine.
In fact, the Molecular Structure Design of blue light material can change its luminous efficiency and thermostability, Chiechi etc. [Adv Mater 2006,18,325] report the fluoranthene derivative 7 of a rigidity, 8,10-triphenyl fluoranthene (TPF), adopts it as blue light material, and this compou nd synthesis is simple, only need two steps, and solid-state, there is higher fluorescence quantum efficiency (0.86).But this structure still exists some shortcomings, as solvability is bad, cause productive rate low, easy crystallization causes film-forming properties bad.Fluorenes is widely used as potential blue light material owing to having large band-gap energy by scientists, and fluorenes has some unique advantages, as high in Heat stability is good, high hole mobility, easily processing treatment, solid state fluorescence quantum yield, therefore enjoy the parent of scientists to look at.
Summary of the invention
One of problem to be solved by this invention be to provide a kind of Heat stability is good, high hole mobility, easily processing treatment, solid state fluorescence quantum yield high containing two fluoranthene organic semiconductor material.
A kind of containing two fluoranthene organic semiconductor material, there is following chemical structural formula:
In formula, R is C
1~ C
12alkyl; Preferred R is C
1~ C
12straight chained alkyl.
Two of problem to be solved by this invention is to provide the above-mentioned preparation method containing two fluoranthene organic semiconductor material, comprises the steps:
S1, by 2,7-bis-trimethylsilyl acetylene-9,9-bis-R base fluorenes, trimethylsilyl acetylene, catalyzer and the first solvent (as, triethylamine) add in reactor, after oil bath heating reflux reaction, generate 2,7-bis-trimethylsilyl acetylene-9,9-dialkyl fluorene; Wherein, be oxygen-free environment in reactor, the mol ratio of 2,7-bis-trimethylsilyl acetylene-9,9-bis-R base fluorenes and trimethylsilyl acetylene is 1: 3;
S2,2,7-bis-trimethylsilyl acetylene-9,9-dialkyl fluorene is dissolved in the mixed solvent filling tetrahydrofuran (THF) and methyl alcohol, then drip alkaline solution (e.g., concentration is the NaOH aqueous solution of 5N), and react in stirred at ambient temperature, obtained 2,7-diacetylene-9,9-dialkyl fluorene;
Under S3, oxygen-free environment, by equimolar 2,7-diacetylene-9,9-dialkyl fluorene and 7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone is dissolved in the second solvent (e.g., dimethylbenzene or o-Xylol), and at 160 DEG C reacting by heating, obtained described containing two fluoranthene organic semiconductor material, its chemical structural formula is as follows:
In formula, R is C
1~ C
12alkyl.
The above-mentioned preparation method containing two fluoranthene organic semiconductor material, in step S1, described catalyzer is the mixture of organic palladium and cuprous iodide, and the mol ratio of organic palladium and cuprous iodide is 2: 1; The ratio of the molar weight of described organic palladium and bromo-9, the 9-dialkyl fluorene molar weights of 2,7-bis-is 0.05 ~ 0.1: 1; The molar weight of described organic palladium and the ratio of 2,7-diacetylene-9,9-dialkyl fluorene molar weight are 0.05 ~ 0.1: 1; Described organic palladium is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride or two (tricyclohexyl phosphine) palladium chloride.
The above-mentioned preparation method containing two fluoranthene organic semiconductor material, in step S1, also comprises the purification process process to 2,7-bis-trimethylsilyl acetylene-9,9-dialkyl fluorene:
After reaction in step S1 is terminated, reaction mixture washed with diethylether is filtered, revolve after desolventizing and be separated using normal hexane as eluent silica gel column chromatography, obtain 2,7-bis-trimethylsilyl acetylene-9,9-dialkyl fluorene of purifying.
The above-mentioned preparation method containing two fluoranthene organic semiconductor material, in step S2, also comprises the purification process process to 2,7-diacetylene-9,9-dialkyl fluorene:
After step S2 reaction terminates, in reaction mixture, add ethyl acetate, then use NaOH excessive in water, bromine cleaning mixture, anhydrous sodium sulfate drying, revolve subsequently and desolventize, obtain 2,7-diacetylene-9,9-bis-R base fluorenes of purifying.
The above-mentioned preparation method containing two fluoranthene organic semiconductor material, in step S3, also comprises the purification process process containing two fluoranthene organic semiconductor material:
After step S3 reaction terminates, reaction mixture is cooled to room temperature, then adds ethanol, filtering-depositing, washing with alcohol throw out, vacuum-drying subsequently, pillar layer separation throw out, what obtain purifying contains two fluoranthene organic semiconductor material.
The above-mentioned obtained emitting layer material that may be used for organic electroluminescence device containing the two fluoranthene organic semiconductor material of fluorenes, especially blue light organic electroluminescence device.
Provided by the invention containing the two fluoranthene organic semiconductor material of fluorenes, this organic semiconductor material has good solubility, and material is readily dissolved in the conventional organic solvent such as tetrahydrofuran (THF), methylene dichloride, toluene, chloroform, is also just easy to processing; This kind of luminescent material, due to the existence of fluoranthene group in structure, makes material have higher hole mobility, and this compounds sends out ethereal blue light simultaneously; Therefore, such material can form efficient, stable blue electroluminescent devices; This material is conducive to the flat-panel monitor and the illuminating device that develop superior performance of future generation.
Provided by the invention containing the two fluoranthene organic semiconductor material preparation method of fluorenes, simple to operate, be easy to control, be convenient to factory and promote.
Accompanying drawing explanation
Fig. 1 is be the fluorescence emission spectra figure of organic semiconductor material D2PFMF film obtained in embodiment 1;
Fig. 2 for executing in example 5, the structural representation of the organic electroluminescence device obtained for luminescent layer with the D2PFMF organic semiconductor material in embodiment 1;
Fig. 3 is the luminance vs. voltage graph of the organic electroluminescence device of embodiment 5.
Embodiment
Provided by the invention containing two fluoranthene organic semiconductor material, be two fluoranthene organic semiconductor material that alkyl chain replaces, it has following chemical structure:
In formula: R is C
1~ C
12alkyl, preferred R is C
1~ C
12straight chained alkyl.
The above-mentioned preparation method containing two fluoranthene organic semiconductor material, comprises the steps:
S1, by structural formula be
2,7-bis-trimethylsilyl acetylene-9,9-bis-R base fluorenes, structural formula be
trimethylsilyl acetylene, catalyzer and the first solvent (e.g., triethylamine, i.e. NEt
3) errorlessly add in reactor, after oil bath heating reflux reaction 48h, generating structure formula is
2,7-bis-trimethylsilyl acetylene-9,9-dialkyl fluorene; Wherein, be oxygen-free environment (i.e. the inert atmosphere of nitrogen and the gas composition of argon gas at least one) in reactor, the mol ratio of 2,7-bis-trimethylsilyl acetylene-9,9-bis-R base fluorenes and trimethylsilyl acetylene is 1: 3; Reaction formula is as follows:
S2, by 2,7-bis-trimethylsilyl acetylene-9,9-dialkyl fluorene is dissolved in the mixed solvent filling tetrahydrofuran (THF) (THF) and methyl alcohol (MeOH), then drip alkaline solution (as, concentration is the NaOH aqueous solution of 5N), and in stirred at ambient temperature reaction 1h, obtained structural formula is
2,7-diacetylene-9,9-dialkyl fluorene; Reaction formula is as follows:
Under S3, oxygen-free environment (i.e. the inert atmosphere of nitrogen and the gas composition of argon gas at least one), by equimolar 2,7-diacetylene-9,9-dialkyl fluorene and structural formula be
7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone be dissolved in the second solvent (e.g., dimethylbenzene or o-Xylol), and at 160 DEG C reacting by heating 24h, obtained described containing two fluoranthene organic semiconductor material, its chemical structural formula is as follows:
in formula, R is C
1~ C
12alkyl; Reaction formula is as follows:
The above-mentioned preparation method containing two fluoranthene organic semiconductor material, in step S1, described catalyzer is the mixture of organic palladium and cuprous iodide, and the mol ratio of organic palladium and cuprous iodide is 2: 1; The molar weight of described organic palladium and the ratio of 2,7-diacetylene-9,9-dialkyl fluorene molar weight are 0.05 ~ 0.1: 1; Described organic palladium is tetrakis triphenylphosphine palladium Pd (PPh
3)
4, two (triphenylphosphine) palladium chloride Pd (PPh
3)
2cl
2, [1,1 '-bis-(diphenylphosphine) ferrocene] palladium chloride Pd (dppf) Cl
2or two (tricyclohexyl phosphine) palladium chloride PdCl
2(PCy
3)
2.
The above-mentioned preparation method containing two fluoranthene organic semiconductor material, in step S1, also comprises the purification process process to 2,7-bis-trimethylsilyl acetylene-9,9-dialkyl fluorene:
After reaction in step S1 is terminated, reaction mixture washed with diethylether is filtered, revolves after desolventizing and be separated using normal hexane as eluent silica gel column chromatography, obtain purifying, light yellow solid, i.e. 2,7-bis-trimethylsilyl acetylene-9,9-dialkyl fluorene.
The above-mentioned preparation method containing two fluoranthene organic semiconductor material, in step S2, also comprises the purification process process to 2,7-diacetylene-9,9-dialkyl fluorene:
After step S2 reaction terminates, in reaction mixture, add ethyl acetate, then use NaOH excessive in water, bromine cleaning mixture, anhydrous sodium sulfate drying, revolve subsequently and desolventize, obtain 2,7-diacetylene-9,9-bis-R base fluorenes of purifying.
The above-mentioned preparation method containing two fluoranthene organic semiconductor material, in step S3, also comprises the purification process process containing two fluoranthene organic semiconductor material:
After step S3 reaction terminates, reaction mixture is cooled to room temperature, then adds ethanol, filtering-depositing, washing with alcohol throw out, vacuum-drying subsequently, pillar layer separation throw out, what obtain purifying contains two fluoranthene organic semiconductor material.
The above-mentioned obtained emitting layer material that may be used for organic electroluminescence device containing the two fluoranthene organic semiconductor material of fluorenes, especially blue light organic electroluminescence device.
Provided by the invention containing the two fluoranthene organic semiconductor material of fluorenes, this organic semiconductor material has good solubility, and material is readily dissolved in the conventional organic solvent such as tetrahydrofuran (THF), methylene dichloride, toluene, chloroform, is also just easy to processing; This kind of luminescent material, due to the existence of fluoranthene group in structure, makes material have higher hole mobility, and this compounds sends out ethereal blue light simultaneously; Therefore, such material can form efficient, stable blue electroluminescent devices; This material is conducive to the flat-panel monitor and the illuminating device that develop superior performance of future generation.
Provided by the invention containing the two fluoranthene organic semiconductor material preparation method of fluorenes, simple to operate, be easy to control, be convenient to factory and promote.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The present embodiment openly following structure containing two fluoranthene organic compound: 2,7-bis-(7,10-phenylbenzene fluoranthene base)-9, the 9-dimethyl fluorenes (D2PFMF) of fluorenes
The preparation of step one: compd A: 2,7-bis-trimethylsilyl acetylene-9,9-dimethyl fluorene
Be connected with in the there-necked flask of nitrogen to one, add catalyst P d (PPh
3)
2cl
2(630mg, 0.9mmol), CuI (45mg, 0.45mmol), 2,7-bis-bromo-9,9-dimethyl fluorene (5.28g, 15mmol), trimethylsilyl acetylene (4.42g, 45mmol), using 60mL triethylamine as solvent, vacuumize logical nitrogen three times, oil bath reflux 48h, washed with diethylether also filters, and revolves and desolventizes, be separated using normal hexane as eluent silica gel column chromatography, obtain light yellow solid (4.5, productive rate 78%).MS：m/z386.
1H NMR(400MHz，CDCl
3)δ(ppm)：7.81(d，2H)，7.70(d，2H)，7.49(t，2H)，1.97(s，6H)，0.19(s，18H)。
The preparation of step 2: 2,7-bis-(7,10-phenylbenzene fluoranthene base)-9,9-dimethyl fluorenes (D2PFMF)
Add in 60mL tetrahydrofuran (THF) and 30mL methanol mixed solvent in compd A, drip 5mLNaOH aqueous solution 5N, reaction mixture is at stirring at room temperature 1h, then extraction into ethyl acetate is added, with water, bromine washing, anhydrous sodium sulfate drying, revolve and desolventize, obtain 2,7-diacetylene-9,9-dimethyl fluorene;
Then compd B (7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g, 30mmol) is added, logical argon gas, add organic solvent o-Xylol 100mL, 160 DEG C (oil baths) heat 24h, after question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, pillar layer separation, obtains product D 2PFMF (10.78g, productive rate 80%).MS：m/z 899.
1H NMR(CD
2Cl
2，400MHz)：7.92-7.68(m，14H)，7.62-7.52(m，14H)，7.46-7.18(m，12H)，2.01(s，6H)。
Fig. 1 is the fluorescence emission spectra figure of organic semiconductor material D2PFMF film in embodiment 1; As seen from Figure 2, D2PFMF sends out blue light good, and blue light maximum emission peak is at 426nm.
Embodiment 2
The present embodiment openly following structure containing two fluoranthene organic compound: 2,7-bis-(7,10-phenylbenzene fluoranthene base)-9, the 9-diethyl fluorenes (D2PFEF) of fluorenes
The preparation of step one: compd A: 2,7-bis-trimethylsilyl acetylene-9,9-diethyl fluorenes
Be connected with in the there-necked flask of argon gas to one, add catalyst P d (PPh
3)
2cl
2(630mg, 0.9mmol), CuI (45mg, 0.45mmol), 2,7-bis-bromo-9,9-diethyl fluorenes (5.70g, 15mmol), trimethylsilyl acetylene (4.42g, 45mmol), using 60mL triethylamine as solvent, vacuumize logical argon gas three times, oil bath reflux 48h, washed with diethylether also filters, and revolves and desolventizes, be separated using normal hexane as eluent silica gel column chromatography, obtain light yellow solid (4.97, productive rate 80%).MS：m/z414.
1H NMR(400MHz，CDCl
3)δ(ppm)：7.81(d，2H)，7.70(d，2H)，7.49(t，2H)，1.97(q，4H)，1.41(t，6H)，0.19(s，18H)。
The preparation of step 2: 2,7-bis-(7,10-phenylbenzene fluoranthene base)-9,9-diethyl fluorenes (D2PFEF)
Add in 60mL tetrahydrofuran (THF) and 30mL methanol mixed solvent in compd A, drip 5mLNaOH aqueous solution 5N, reaction mixture is at stirring at room temperature 1h, then extraction into ethyl acetate is added, with water, bromine washing, anhydrous sodium sulfate drying, revolve and desolventize, obtain 2,7-diacetylene-9,9-diethyl fluorenes.
Then compd B (7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g, 30mmol) is added, logical argon gas, add organic solvent o-Xylol 100mL, 160 DEG C (oil baths) heat 24h, after question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, pillar layer separation, obtains product D 2PFEF (10.8g, productive rate 78%).MS：m/z 926.
1H NMR(CD
2Cl
2，400MHz)：7.91-7.68(m，14H)，7.62-7.52(m，14H)，7.46-7.18(m，12H)，1.98(q，4H)，1.42(t，6H)。
Embodiment 3
The present embodiment openly following structure containing two fluoranthene organic compound: 2,7-bis-(7,10-phenylbenzene fluoranthene base)-9, the 9-dihexyl fluorenes (D2PFHF) of fluorenes
The preparation of step one: compd A: 2,7-bis-trimethylsilyl acetylene-9,9-hexyl fluorenes
Be connected with in the there-necked flask of the gas mixture of nitrogen and argon gas to one, add catalyst P d (PPh
3)
2cl
2(630mg, 0.9mmol), CuI (45mg, 0.45mmol), 2,7-bis-bromo-9,9-hexyl fluorenes (7.38g, 15mmol), trimethylsilyl acetylene (4.42g, 45mmol), using 60mL triethylamine as solvent, vacuumize the gas mixture three times of logical nitrogen and argon gas, oil bath reflux 48h, washed with diethylether also filters, and revolves and desolventizes, be separated using normal hexane as eluent silica gel column chromatography, obtain light yellow solid (6.0, productive rate 76%).MS：m/z526.
1H NMR(400MHz，CDCl
3)δ(ppm)：7.81(d，2H)，7.70(d，2H)，7.49(t，2H)，1.97(q，4H)，1.21-1.46(m，22H)，0.19(s，18H)。
The preparation of step 2: 2,7-bis-(7,10-phenylbenzene fluoranthene base)-9,9-dihexyl fluorenes (D2PFHF)
Add in 60mL tetrahydrofuran (THF) and 30mL methanol mixed solvent in compd A, drip 5mLNaOH aqueous solution 5N, reaction mixture is at stirring at room temperature 1h, then extraction into ethyl acetate is added, with water, bromine washing, anhydrous sodium sulfate drying, revolve and desolventize, obtain 2,7-diacetylene-9,9-dihexyl fluorenes.
Then compd B (7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g, 30mmol) is added, the gas mixture of logical nitrogen and argon gas, add organic solvent o-Xylol 100mL, 160 DEG C (oil baths) heat 24h, after question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, pillar layer separation, obtains product D 2PFHF (12.46g, productive rate 80%).MS：m/z 1038.
1H NMR(CD
2Cl
2，400MHz)：7.91-7.68(m，14H)，7.62-7.52(m，14H)，7.46-7.18(m，12H)，2.01(q，4H)，1.21-1.47(m，22H)。
Embodiment 4
The present embodiment openly following structure containing two fluoranthene organic compound: 2,7-bis-(7,10-phenylbenzene fluoranthene base)-9, the 9-docosyl fluorenes (D2PFDF) of fluorenes
The preparation of step one: compd A: 2,7-bis-trimethylsilyl acetylene-9,9-docosyl fluorenes
Be connected with in the there-necked flask of nitrogen to one, add catalyst P d (PPh
3)
2cl
2(630mg, 0.9mmol), CuI (45mg, 0.45mmol), 2,7-bis-bromo-9,9-docosyl fluorenes (9.9g, 15mmol), trimethylsilyl acetylene (4.42g, 45mmol), using 60mL triethylamine as solvent, vacuumize logical nitrogen three times, oil bath reflux 48h, washed with diethylether also filters, and revolves and desolventizes, be separated using normal hexane as eluent silica gel column chromatography, obtain light yellow solid (7.9, productive rate 76%).MS：m/z695.
1H NMR(400MHz，CDCl
3)δ(ppm)：7.81(d，2H)，7.70(d，2H)，7.49(t，2H)，1.97(q，4H)，1.21-1.76(m，，46H)，0.19(s，18H)。
The preparation of step 2: 2,7-bis-(7,10-phenylbenzene fluoranthene base)-9,9-docosyl fluorenes (D2PFDF)
Add in 60mL tetrahydrofuran (THF) and 30mL methanol mixed solvent in compd A, drip 5mLNaOH aqueous solution 5N, reaction mixture is at stirring at room temperature 1h, then extraction into ethyl acetate is added, with water, bromine washing, anhydrous sodium sulfate drying, revolve and desolventize, obtain 2,7-diacetylene-9,9-docosyl fluorenes;
Then compd B (7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g, 30mmol) is added, logical argon gas, add organic solvent o-Xylol 100mL, 160 DEG C (oil baths) heat 24h, after question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, pillar layer separation, obtains product D 2PFDF (13.58g, productive rate 75%).MS：m/z 1207.
1H NMR(CD
2Cl
2，400MHz)：7.91-7.68(m，14H)，7.62-7.52(m，14H)，7.46-7.18(m，12H)，2.01(q，4H)，1.21-1.47(m，46H)。
Embodiment 5
The emitting layer material of the organic electroluminescence device of the present embodiment adopts embodiment 1 obtained containing two fluoranthene organic compound: 2,7-bis-(7,10-phenylbenzene fluoranthene base)-9, the 9-dimethyl fluorenes (D2PFMF) of fluorenes.Its preparation technology is as follows:
1, by ito glass spin coating photoresist material, exposure, development, chloroazotic acid etching, be etched into required pattern and size, then the conductive glass cleaning will etched, use each ultrasonic cleaning 15min such as pure water, acetone, ethanol successively, clean up and rear oxygen plasma treatment is carried out to it, the oxygen plasma treatment time is 15min, and power is 35W, improves the surperficial work content of conductive glass with this;
2, ito glass is put into organic vacuum cavity, (material is m-MTDATA:F4-TCNQ to stack gradually evaporation p-doping hole transmission layer on the ito layer, thickness is 40nm), (material is D2PFMF to luminescent layer, thickness is 30nm), (material is Bphen to hole blocking layer, thickness is 10nm), n-adulterates, and (material is Bphen:Cs to electron transfer layer, and Cs adulterates in Bphen; Thickness is 40nm);
3, then the substrate of step 2 is moved into metallic cavity, continue evaporation cathode layer magnesium silver alloys Mg: Ag (10: 1, wt%) 150nm, the Ag layer of last evaporation one deck 10nm;
Obtain required high efficiency blue organic electroluminescence device.
As shown in Figure 2, this blue light organic electroluminescence device structure is: glass/ITO/m-MTDATA:F4-TCNQ/D2PFMF/Bphen/Bphen:Cs/Mg:Ag/Ag.
Above-mentioned m-MTDATA is 4,4 ', 4, and "-three (3-aminomethyl phenyl aniline) triphenylamine, F4-TCNQ is tetrafluoro para benzoquinone bismethane, and Bphen is 4,7-phenylbenzene-1,10-phenanthroline.
Fig. 3 is the luminance vs. voltage graph of the organic electroluminescence device of embodiment 5; As shown in Figure 3, the trigger voltage of this organic electroluminescence device is 3.7V(1cd/m
2), high-high brightness is 29042cd/m
2.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (8)
1., containing a preparation method for two fluoranthene organic semiconductor material, it is characterized in that, comprise the steps:
S1,2,7-bis-trimethylsilyl acetylene-9,9-bis-R base fluorenes, trimethylsilyl acetylene, catalyzer and the first solvent are added in reactor, after oil bath heating reflux reaction, generate 2,7-bis-trimethylsilyl acetylene-9,9-dialkyl fluorene; Wherein, be oxygen-free environment in reactor, the mol ratio of 2,7-bis-trimethylsilyl acetylene-9,9-bis-R base fluorenes and trimethylsilyl acetylene is 1:3;
S2,2,7-bis-trimethylsilyl acetylene-9,9-dialkyl fluorene to be dissolved in the mixed solvent filling tetrahydrofuran (THF) and methyl alcohol, then to drip alkaline solution, and in stirred at ambient temperature reaction, obtained 2,7-diacetylene-9,9-dialkyl fluorene;
Under S3, oxygen-free environment, by equimolar 2,7-diacetylenes-9,9-dialkyl fluorene and 7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone are dissolved in the second solvent, and at 160 DEG C reacting by heating, obtained described containing two fluoranthene organic semiconductor material, its chemical structural formula is as follows:
In formula, R is C
1~ C
12alkyl.
2. the preparation method containing two fluoranthene organic semiconductor material according to claim 1, it is characterized in that, in step S1, the first solvent is triethylamine; Described catalyzer is the mixture of organic palladium and cuprous iodide, and the mol ratio of organic palladium and cuprous iodide is 2:1; The ratio of the molar weight of described organic palladium and bromo-9, the 9-dialkyl fluorene molar weights of 2,7-bis-is 0.05 ~ 0.1:1.
3. the preparation method containing two fluoranthene organic semiconductor material according to claim 1, it is characterized in that, described organic palladium is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, [two (diphenylphosphine) ferrocene of 1,1'-] palladium chloride or two (tricyclohexyl phosphine) palladium chloride.
4. the preparation method containing two fluoranthene organic semiconductor material according to claim 1, is characterized in that, in step S1, also comprise the purification process process to 2,7-bis-trimethylsilyl acetylene-9,9-dialkyl fluorene:
After reaction in step S1 is terminated, reaction mixture washed with diethylether is filtered, revolve after desolventizing and be separated using normal hexane as eluent silica gel column chromatography, obtain 2,7-bis-trimethylsilyl acetylene-9,9-dialkyl fluorene of purifying.
5. the preparation method containing two fluoranthene organic semiconductor material according to claim 1, is characterized in that, in step S2, and the NaOH aqueous solution of described alkaline solution to be concentration be 5N.
6. the preparation method containing two fluoranthene organic semiconductor material according to claim 1, is characterized in that, in step S2, also comprise the purification process process to 2,7-diacetylene-9,9-dialkyl fluorene:
After step S2 reaction terminates, in reaction mixture, add extraction into ethyl acetate, then use NaOH excessive in water, bromine cleaning mixture, anhydrous sodium sulfate drying, revolve subsequently and desolventize, obtain 2,7-diacetylene-9,9-bis-R base fluorenes of purifying.
7. the preparation method containing two fluoranthene organic semiconductor material according to claim 1, it is special
Levy and be, in step S3, the second solvent is p-Xylol or o-Xylol.
8. the preparation method containing two fluoranthene organic semiconductor material according to claim 1, is characterized in that, in step S3, also comprises the purification process process containing two fluoranthene organic semiconductor material:
After step S3 reaction terminates, reaction mixture is cooled to room temperature, then adds ethanol, filtering-depositing, washing with alcohol throw out, vacuum-drying subsequently, pillar layer separation throw out, what obtain purifying contains two fluoranthene organic semiconductor material.
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