CN103159584A - 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 as the following, 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 the organic semiconductor material field, relate in particular to a kind of two fluoranthene organic semiconductor material and its preparation method and application that contain.
Background technology
1987, the Tang of U.S. Eastman Kodak company and VanSlyke reported the breakthrough in 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) make up and prepared 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 over 1000 hours.This landmark work makes people see the practical and business-like rosy prospect of organic electroluminescent.
In recent years, have efficient, energy-conservation Organic Light Emitting Diode and caused people's interest widely in demonstration field and lighting field.Realize the application purposes such as panchromatic demonstration and illumination, blue light is absolutely necessary in three primary colours.Simultaneously, because the blue light energy is the highest, material just can obtain green glow and ruddiness by several different methods as long as have preferably.Therefore the luminescent properties that improves blue light is significant to realizing the panchromatic demonstration of organic electroluminescent and solid luminescence.But because the energy of blue light is high, efficient 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] have reported 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 needed for two steps, and have a higher fluorescence quantum efficiency (0.86) solid-state.Yet still there are some shortcomings in this structure, and is as bad in solvability, causes productive rate low, and easily crystallization causes film-forming properties bad etc.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 Heat stability is good, high hole mobility, easily processing treatment, solid state fluorescence quantum yield are high, 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 contain two fluoranthene organic semiconductor material.
A kind of pair fluoranthene organic semiconductor material that contain have 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 who contains two fluoranthene organic semiconductor material, comprises the steps:
S1, with 2,7-, two trimethylsilyl acetylenes-9,9-two R base fluorenes, trimethylsilyl acetylene, catalyzer and the first solvent (as, triethylamine) add in reactor, after the oil bath heating reflux reaction, generate 2,7-, two trimethylsilyl acetylenes-9,9-dialkyl group fluorenes; Wherein, be oxygen-free environment in reactor, 2,7-, two trimethylsilyl acetylenes-9, the mol ratio of 9-two R base fluorenes and trimethylsilyl acetylene is 1: 3;
S2, with 2,7-, two trimethylsilyl acetylenes-9,9-dialkyl group fluorenes is dissolved in the mixed solvent that fills tetrahydrofuran (THF) and methyl alcohol, then drip alkaline solution (as, concentration is the NaOH aqueous solution of 5N), and under room temperature stirring reaction, make 2,7-diacetylene-9,9-dialkyl group fluorenes;
Under S3, oxygen-free environment, with equimolar 2,7-diacetylene-9,9-dialkyl group fluorenes and 7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone be dissolved in the second solvent (as, dimethylbenzene or o-Xylol) in, and 160 ℃ of lower reacting by heating, make described two fluoranthene organic semiconductor material that contain, its chemical structural formula is as follows:
In formula, R is C
1～C
12Alkyl.
The above-mentioned preparation method who contains 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 2,7-, two bromo-9, the ratio of 9-dialkyl group fluorenes molar weight is 0.05～0.1: 1; The molar weight of described organic palladium and 2,7-diacetylene-9, the ratio of 9-dialkyl group fluorenes molar weight is 0.05～0.1: 1; Described organic palladium is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, [1,1 '-two (diphenylphosphine) ferrocene] palladium chloride or two (tricyclohexyl phosphine) palladium chloride.
The above-mentioned preparation method who contains two fluoranthene organic semiconductor material in step S1, also comprises two trimethylsilyl acetylenes-9 to 2,7-, the purification process process of 9-dialkyl group fluorenes:
After in step S1, reaction finishes, reaction mixture is washed and filters with ether, revolve to desolventize afterwards and separate as the eluent silica gel column chromatography with normal hexane, obtain 2 of purifying, 7-two trimethylsilyl acetylenes-9,9-dialkyl group fluorenes.
The above-mentioned preparation method who contains two fluoranthene organic semiconductor material in step S2, also comprises to 2,7-diacetylene-9 the purification process process of 9-dialkyl group fluorenes:
After step S2 reaction finishes, add ethyl acetate toward reaction mixture in, excessive NaOH in water, bromine cleaning mixture then, anhydrous sodium sulfate drying revolves subsequently and desolventizes, and obtains 2 of purifying, 7-diacetylene-9, the basic fluorenes of 9-two R.
The above-mentioned preparation method who contains two fluoranthene organic semiconductor material in step S3, also comprises containing the purification process process of two fluoranthene organic semiconductor material:
After step S3 reaction finishes, reaction mixture is cooled to room temperature, then adds ethanol, filtering-depositing, the washing with alcohol throw out, vacuum-drying subsequently, column chromatography sediment separate out obtain containing of purifying of two fluoranthene organic semiconductor material.
Above-mentioned making contains luminescent layer material, the especially blue light organic electroluminescence device that the two fluoranthene organic semiconductor material of fluorenes can be used for organic electroluminescence device.
The two fluoranthene organic semiconductor material of fluorenes that contain provided by the invention, this organic semiconductor material has good solubility, and material is soluble in the organic solvent that tetrahydrofuran (THF), methylene dichloride, toluene, chloroform etc. are commonly used, and also just is easy to processing; This class luminescent material makes material have higher hole mobility due to the existence of fluoranthene group in structure, and this compounds is sent out ethereal blue light simultaneously; Therefore, such material can form efficient, stable blue electroluminescent devices; This material is conducive to develop flat-panel monitor and the illuminating device of superior performance of future generation.
The two fluoranthene organic semiconductor material preparation methods of fluorenes that contain provided by the invention, simple to operate, be easy to control, be convenient to factory and promote.
Description of drawings
Fig. 1 is to be the fluorescence radiation spectrogram of the organic semiconductor material D2PFMF film that makes in embodiment 1;
Fig. 2 is for executing in example 5, the structural representation of the organic electroluminescence device that the D2PFMF organic semiconductor material in the embodiment 1 makes as luminescent layer;
Fig. 3 is the brightness-voltage curve of the organic electroluminescence device of embodiment 5.
Embodiment
Pair fluoranthene organic semiconductor material that contain provided by the invention are two fluoranthene organic semiconductor material that alkyl chain replaces, and 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 who contains two fluoranthene organic semiconductor material comprises the steps:
S1, with structural formula be
2,7-two trimethylsilyl acetylenes-9,9-two R base fluorenes, structural formula are
Trimethylsilyl acetylene, catalyzer and the first solvent (as, triethylamine, i.e. NEt
3) errorless adding in reactor, after oil bath heating reflux reaction 48h, the generating structure formula is
2,7-two trimethylsilyl acetylenes-9,9-dialkyl group fluorenes; Wherein, be oxygen-free environment (being the inert atmosphere of nitrogen and at least a gas composition of argon gas) in reactor, 2,7-, two trimethylsilyl acetylenes-9, the mol ratio of 9-two R base fluorenes and trimethylsilyl acetylene is 1: 3; Reaction formula is as follows:
S2, with 2,7-, two trimethylsilyl acetylenes-9,9-dialkyl group fluorenes is dissolved in the mixed solvent that fills tetrahydrofuran (THF) (THF) and methyl alcohol (MeOH), then drip alkaline solution (as, concentration is the NaOH aqueous solution of 5N), and under room temperature stirring reaction 1h, make structural formula and be
2,7-diacetylene-9,9-dialkyl group fluorenes; Reaction formula is as follows:
Under S3, oxygen-free environment (being the inert atmosphere of nitrogen and at least a gas composition of argon gas), with equimolar 2,7-diacetylene-9,9-dialkyl group fluorenes and structural formula are
7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone be dissolved in the second solvent (as, dimethylbenzene or o-Xylol) in, and at 160 ℃ of lower reacting by heating 24h, make described two fluoranthene organic semiconductor material that contain, 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 who contains 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 2,7-diacetylene-9, the ratio of 9-dialkyl group fluorenes molar weight is 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 '-two (diphenylphosphine) ferrocene] palladium chloride Pd (dppf) Cl
2Perhaps two (tricyclohexyl phosphine) palladium chloride PdCl
2(PCy
3)
2
The above-mentioned preparation method who contains two fluoranthene organic semiconductor material in step S1, also comprises two trimethylsilyl acetylenes-9 to 2,7-, the purification process process of 9-dialkyl group fluorenes:
After reaction in step S1 is finished, reaction mixture wash and filters with ether, revolve and desolventize afterwards with normal hexane as the separation of eluent silica gel column chromatography, obtain purifying, light yellow solid, namely 2,7-two trimethylsilyl acetylenes-9,9-dialkyl group fluorenes.
The above-mentioned preparation method who contains two fluoranthene organic semiconductor material in step S2, also comprises to 2,7-diacetylene-9 the purification process process of 9-dialkyl group fluorenes:
After step S2 reaction finishes, add ethyl acetate toward reaction mixture in, excessive NaOH in water, bromine cleaning mixture then, anhydrous sodium sulfate drying revolves subsequently and desolventizes, and obtains 2 of purifying, 7-diacetylene-9, the basic fluorenes of 9-two R.
The above-mentioned preparation method who contains two fluoranthene organic semiconductor material in step S3, also comprises containing the purification process process of two fluoranthene organic semiconductor material:
After step S3 reaction finishes, reaction mixture is cooled to room temperature, then adds ethanol, filtering-depositing, the washing with alcohol throw out, vacuum-drying subsequently, column chromatography sediment separate out obtain containing of purifying of two fluoranthene organic semiconductor material.
Above-mentioned making contains luminescent layer material, the especially blue light organic electroluminescence device that the two fluoranthene organic semiconductor material of fluorenes can be used for organic electroluminescence device.
The two fluoranthene organic semiconductor material of fluorenes that contain provided by the invention, this organic semiconductor material has good solubility, and material is soluble in the organic solvent that tetrahydrofuran (THF), methylene dichloride, toluene, chloroform etc. are commonly used, and also just is easy to processing; This class luminescent material makes material have higher hole mobility due to the existence of fluoranthene group in structure, and this compounds is sent out ethereal blue light simultaneously; Therefore, such material can form efficient, stable blue electroluminescent devices; This material is conducive to develop flat-panel monitor and the illuminating device of superior performance of future generation.
The two fluoranthene organic semiconductor material preparation methods of fluorenes that contain provided by the invention, 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
What the present embodiment disclosed following structure contains two fluoranthene organic compound: 2, the 7-two (7,10-phenylbenzene fluoranthene base)-9 of fluorenes, 9-dimethyl fluorene (D2PFMF)
Step 1: compd A: 2,7-two trimethylsilyl acetylenes-9, the preparation of 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-, two bromo-9,9-dimethyl fluorene (5.28g, 15mmol), trimethylsilyl acetylene (4.42g, 45mmol), as solvent, vacuumize logical nitrogen three times with the 60mL triethylamine, oil bath reflux 48h, ether washs and filters, and revolves to desolventize, separate as the eluent silica gel column chromatography with normal hexane, 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)。
Step 2: 2,7-two (7,10-phenylbenzene fluoranthene base)-9, the preparation of 9-dimethyl fluorene (D2PFMF)
Add in compd A in 60mL tetrahydrofuran (THF) and 30mL methanol mixed solvent, drip 5mLNaOH aqueous solution 5N, reaction mixture is at stirring at room 1h, then add ethyl acetate extraction, water, bromine washing, anhydrous sodium sulfate drying, revolve and desolventize, obtain 2,7-diacetylene-9, the 9-dimethyl fluorene;
Then add compd B (7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g, 30mmol), logical argon gas adds organic solvent o-Xylol 100mL, 160 ℃ (oil bath) heating 24h, after the question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, column chromatography is separated, and 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 radiation spectrogram of organic semiconductor material D2PFMF film in embodiment 1; As seen from Figure 2, D2PFMF sends out blue light good, and the blue light maximum emission peak is at 426nm.
Embodiment 2
What the present embodiment disclosed following structure contains two fluoranthene organic compound: 2, the 7-two (7,10-phenylbenzene fluoranthene base)-9 of fluorenes, 9-diethyl fluorenes (D2PFEF)
Step 1: compd A: 2,7-two trimethylsilyl acetylenes-9, the preparation of 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-, two bromo-9,9-diethyl fluorenes (5.70g, 15mmol), trimethylsilyl acetylene (4.42g, 45mmol), as solvent, vacuumize logical argon gas three times with the 60mL triethylamine, oil bath reflux 48h, ether washs and filters, and revolves to desolventize, separate as the eluent silica gel column chromatography with normal hexane, 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)。
Step 2: 2,7-two (7,10-phenylbenzene fluoranthene base)-9, the preparation of 9-diethyl fluorenes (D2PFEF)
Add in compd A in 60mL tetrahydrofuran (THF) and 30mL methanol mixed solvent, drip 5mLNaOH aqueous solution 5N, reaction mixture is at stirring at room 1h, then add ethyl acetate extraction, water, bromine washing, anhydrous sodium sulfate drying, revolve and desolventize, obtain 2,7-diacetylene-9,9-diethyl fluorenes.
Then add compd B (7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g, 30mmol), logical argon gas adds organic solvent o-Xylol 100mL, 160 ℃ (oil bath) heating 24h, after the question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, column chromatography is separated, and 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
What the present embodiment disclosed following structure contains two fluoranthene organic compound: 2, the 7-two (7,10-phenylbenzene fluoranthene base)-9 of fluorenes, 9-dihexyl fluorenes (D2PFHF)
Step 1: compd A: 2,7-two trimethylsilyl acetylenes-9, the preparation of 9-hexyl fluorenes
Be connected with in the there-necked flask of 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-, two bromo-9,9-hexyl fluorenes (7.38g, 15mmol), trimethylsilyl acetylene (4.42g, 45mmol), as solvent, vacuumize the gas mixture three times of logical nitrogen and argon gas with the 60mL triethylamine, oil bath reflux 48h, ether washs and filters, and revolves to desolventize, separate as the eluent silica gel column chromatography with normal hexane, 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)。
Step 2: 2,7-two (7,10-phenylbenzene fluoranthene base)-9, the preparation of 9-dihexyl fluorenes (D2PFHF)
Add in compd A in 60mL tetrahydrofuran (THF) and 30mL methanol mixed solvent, drip 5mLNaOH aqueous solution 5N, reaction mixture is at stirring at room 1h, then add ethyl acetate extraction, water, bromine washing, anhydrous sodium sulfate drying, revolve and desolventize, obtain 2,7-diacetylene-9,9-dihexyl fluorenes.
Then add compd B (7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g, 30mmol), the gas mixture of logical nitrogen and argon gas adds organic solvent o-Xylol 100mL, 160 ℃ (oil bath) heating 24h, after the question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, column chromatography is separated, and 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
What the present embodiment disclosed following structure contains two fluoranthene organic compound: 2, the 7-two (7,10-phenylbenzene fluoranthene base)-9 of fluorenes, 9-docosyl fluorenes (D2PFDF)
Step 1: compd A: 2,7-two trimethylsilyl acetylenes-9, the preparation of 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-, two bromo-9,9-docosyl fluorenes (9.9g, 15mmol), trimethylsilyl acetylene (4.42g, 45mmol), as solvent, vacuumize logical nitrogen three times with the 60mL triethylamine, oil bath reflux 48h, ether washs and filters, and revolves to desolventize, separate as the eluent silica gel column chromatography with normal hexane, 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)。
Step 2: 2,7-two (7,10-phenylbenzene fluoranthene base)-9, the preparation of 9-docosyl fluorenes (D2PFDF)
Add in compd A in 60mL tetrahydrofuran (THF) and 30mL methanol mixed solvent, drip 5mLNaOH aqueous solution 5N, reaction mixture is at stirring at room 1h, then add ethyl acetate extraction, water, bromine washing, anhydrous sodium sulfate drying, revolve and desolventize, obtain 2,7-diacetylene-9,9-docosyl fluorenes;
Then add compd B (7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone) (10.68g, 30mmol), logical argon gas adds organic solvent o-Xylol 100mL, 160 ℃ (oil bath) heating 24h, after the question response mixed solution is cooled to room temperature, add ethanol, filtering-depositing, washing with alcohol, vacuum-drying, column chromatography is separated, and 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)。
The luminescent layer material employing embodiment 1 of the organic electroluminescence device of the present embodiment makes and contains two fluoranthene organic compound: 2, the 7-two (7,10-phenylbenzene fluoranthene base)-9 of fluorenes, 9-dimethyl fluorene (D2PFMF).Its preparation technology is as follows:
1, with ito glass spin coating photoresist material, exposure, development, chloroazotic acid etching, be etched into needed pattern and size, then the conductive glass that etching is good cleans, use successively each ultrasonic cleaning 15min such as pure water, acetone, ethanol, clean up and rear 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;
2, ito glass is put into the 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), (material is Bphen:Cs to n-doping electron transfer layer, and in Cs doping 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 needed efficient blue light 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 " three (3-aminomethyl phenyl aniline) triphenylamine, F4-TCNQ is tetrafluoro four cyano para benzoquinone bismethane, Bphen is 4,7-phenylbenzene-1, the 10-phenanthroline.
Fig. 3 is the brightness-voltage curve 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, above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. one kind contains two fluoranthene organic semiconductor material, it is characterized in that having following chemical structural formula:
In formula, R is C
1～C
12Straight chained alkyl.
2. a preparation method who contains two fluoranthene organic semiconductor material, is characterized in that, comprises the steps:
S1, with 2,7-, two trimethylsilyl acetylenes-9,9-two R base fluorenes, trimethylsilyl acetylene, catalyzer and the first solvent add in reactor, after the oil bath heating reflux reaction, generate 2,7-, two trimethylsilyl acetylenes-9,9-dialkyl group fluorenes; Wherein, be oxygen-free environment in reactor, 2,7-, two trimethylsilyl acetylenes-9, the mol ratio of 9-two R base fluorenes and trimethylsilyl acetylene is 1: 3;
S2, with 2,7-, two trimethylsilyl acetylenes-9,9-dialkyl group fluorenes is dissolved in the mixed solvent that fills tetrahydrofuran (THF) and methyl alcohol, then drips alkaline solution, and under room temperature stirring reaction, make 2,7-diacetylene-9,9-dialkyl group fluorenes;
Under S3, oxygen-free environment, with equimolar 2,7-diacetylene-9,9-dialkyl group fluorenes and 7,9-phenylbenzene-cyclopentenes naphthalene-8-ketone is dissolved in the second solvent, and 160 ℃ of lower reacting by heating, make described two fluoranthene organic semiconductor material that contain, its chemical structural formula is as follows:
In formula, R is C
1～C
12Alkyl.
3. the preparation method who contains two fluoranthene organic semiconductor material according to claim 2, 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 molar weight of described organic palladium and 2,7-, two bromo-9, the ratio of 9-dialkyl group fluorenes molar weight is 0.05～0.1: 1.
4. the preparation method who contains two fluoranthene organic semiconductor material according to claim 3, it is characterized in that, described organic palladium is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, [1,1 '-two (diphenylphosphine) ferrocene] palladium chloride or two (tricyclohexyl phosphine) palladium chloride.
5. the preparation method who contains two fluoranthene organic semiconductor material according to claim 2, is characterized in that, in step S1, also comprises two trimethylsilyl acetylenes-9 to 2,7-, the purification process process of 9-dialkyl group fluorenes:
After in step S1, reaction finishes, reaction mixture is washed and filters with ether, revolve to desolventize afterwards and separate as the eluent silica gel column chromatography with normal hexane, obtain 2 of purifying, 7-two trimethylsilyl acetylenes-9,9-dialkyl group fluorenes.
6. the preparation method who contains two fluoranthene organic semiconductor material according to claim 2, is characterized in that, in step S2, described alkaline solution is that concentration is the NaOH aqueous solution of 5N.
7. the preparation method who contains two fluoranthene organic semiconductor material according to claim 2, is characterized in that, in step S2, also comprises to 2,7-diacetylene-9 the purification process process of 9-dialkyl group fluorenes:
After step S2 reaction finishes, add ethyl acetate extraction toward reaction mixture in, excessive NaOH in water, bromine cleaning mixture then, anhydrous sodium sulfate drying revolves subsequently and desolventizes, and obtains 2 of purifying, 7-diacetylene-9, the basic fluorenes of 9-two R.
8. the preparation method who contains two fluoranthene organic semiconductor material according to claim 2, is characterized in that, in step S3, the second solvent is p-Xylol or o-Xylol.
9. the preparation method who contains two fluoranthene organic semiconductor material according to claim 2, is characterized in that, in step S3, also comprises containing the purification process process of two fluoranthene organic semiconductor material:
After step S3 reaction finishes, reaction mixture is cooled to room temperature, then adds ethanol, filtering-depositing, the washing with alcohol throw out, vacuum-drying subsequently, column chromatography sediment separate out obtain containing of purifying of two fluoranthene organic semiconductor material.
10. claim 1 is described contains the two application of fluoranthene organic semiconductor material in the luminescent layer of organic electroluminescence device.
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| CN1366792A (en) * | 2000-03-30 | 2002-08-28 | 出光兴产株式会社 | Organic electroluminescent device and organic light-emitting medium |
| CN1571763A (en) * | 2002-08-27 | 2005-01-26 | 佳能株式会社 | Fluorene compound and organic lumnescent device using the same |
| WO2008059713A1 (en) * | 2006-11-15 | 2008-05-22 | Idemitsu Kosan Co., Ltd. | Fluoranthene compound, organic electroluminescent device using the fluoranthene compound, and organic electroluminescent material-containing solution |
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| CN1366792A (en) * | 2000-03-30 | 2002-08-28 | 出光兴产株式会社 | Organic electroluminescent device and organic light-emitting medium |
| CN1571763A (en) * | 2002-08-27 | 2005-01-26 | 佳能株式会社 | Fluorene compound and organic lumnescent device using the same |
| WO2008059713A1 (en) * | 2006-11-15 | 2008-05-22 | Idemitsu Kosan Co., Ltd. | Fluoranthene compound, organic electroluminescent device using the fluoranthene compound, and organic electroluminescent material-containing solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109810130A (en) * | 2019-03-19 | 2019-05-28 | 合肥学院 | A kind of rigidity line style C60Photosensitive chemoattractant molecule of the glimmering triplet of fluorine boron and preparation method thereof |
| CN109810130B (en) * | 2019-03-19 | 2021-12-07 | 合肥学院 | Rigid linear C60-fluoroboric fluorescent triplet-state photosensitized molecule and preparation method thereof |
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