CN102295757B - Carbazolyl porphyrin-thienopyrazine-containing copolymer and preparation method as well as application thereof - Google Patents
Carbazolyl porphyrin-thienopyrazine-containing copolymer and preparation method as well as application thereof Download PDFInfo
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- CN102295757B CN102295757B CN 201010211534 CN201010211534A CN102295757B CN 102295757 B CN102295757 B CN 102295757B CN 201010211534 CN201010211534 CN 201010211534 CN 201010211534 A CN201010211534 A CN 201010211534A CN 102295757 B CN102295757 B CN 102295757B
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- porphyrin
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- carbazolyl
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- 0 CBrC([C@@]1NC(C(c2ccc(c3ccccc3[n]3*)c3c2)=C2N=C3C=C2)=CC1)=C(C=C1)N=C1C([C@]1C=C2N(*)c4ccccc4C2=CC1)=C(C=C1)NC1=C3Br Chemical compound CBrC([C@@]1NC(C(c2ccc(c3ccccc3[n]3*)c3c2)=C2N=C3C=C2)=CC1)=C(C=C1)N=C1C([C@]1C=C2N(*)c4ccccc4C2=CC1)=C(C=C1)NC1=C3Br 0.000 description 5
- PXLKMCKZIVMRAH-CLTKARDFSA-N C=C/C=C\NC1=CC=C1 Chemical compound C=C/C=C\NC1=CC=C1 PXLKMCKZIVMRAH-CLTKARDFSA-N 0.000 description 1
- BRJJKXFAYZCXRD-UHFFFAOYSA-N CC1(C)OB(c([s]2)c3nccnc3c2S2OC(C)(C)C(C)(C)O2)OC1(C)C Chemical compound CC1(C)OB(c([s]2)c3nccnc3c2S2OC(C)(C)C(C)(C)O2)OC1(C)C BRJJKXFAYZCXRD-UHFFFAOYSA-N 0.000 description 1
- DGGHZXTZLNSRCR-WBFGVMTOSA-N CCCCCCCC[n]1c2cc(/C(/c3ccc(/C(/[BrH]C)=C4\N=C5C=C4)[nH]3)=C(\C=C3)/N=C3/C(/[BrH]C)=C(/C=C3)\N/C3=C5/c3ccc(c(cccc4)c4[n]4CCCCCCCC)c4c3)ccc2c2ccccc12 Chemical compound CCCCCCCC[n]1c2cc(/C(/c3ccc(/C(/[BrH]C)=C4\N=C5C=C4)[nH]3)=C(\C=C3)/N=C3/C(/[BrH]C)=C(/C=C3)\N/C3=C5/c3ccc(c(cccc4)c4[n]4CCCCCCCC)c4c3)ccc2c2ccccc12 DGGHZXTZLNSRCR-WBFGVMTOSA-N 0.000 description 1
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention belongs to the field of photoelectric materials, and discloses carbazolyl porphyrin-thienopyrazine-containing copolymer. The polymer has a structural formula (I), wherein n is an integer of 1-100; and R1 and R2 are the same or different hydrogen or C1-C32 alkyl groups. The invention also discloses a preparation method and application of the carbazolyl porphyrin-thienopyrazine-containing copolymer. In the carbazolyl porphyrin-thienopyrazine-containing copolymer provided by the invention, the solubility property of the material is improved by introducing long-chain alkyl group; meanwhile, filming processing is facilitated; and an application range of the copolymer in the fields of polymer solar cells and the like is expanded.
Description
Technical field
The present invention relates to a kind of multipolymer, relate to more specifically a kind of carbazolyl porphyrin-thienopyrazine multipolymer that contains.
The invention still further relates to the preparation method and the application thereof that contain carbazolyl porphyrin-thienopyrazine multipolymer.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.Be used at present the silicon wafer battery on ground owing to complex manufacturing, cost are high, its application is restricted.In order to reduce the battery cost, expand range of application, people are seeking novel solar cell material always for a long time.Organic semiconductor material with its raw material be easy to get, cheap, preparation technology is simple, environmental stability good, have the good advantages such as photovoltaic effect to receive much concern.From N.S.Sariciftci in 1992 etc. at SCIENCE (N.S Sariciftci, L.Smilowitz, A.J.Heeger, etal.Science, 1992,258,1474) upper report conjugated polymers and C
60Between the Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar battery, and have obtained development at full speed, but still much lower than the efficiency of conversion of inorganic solar cell.The main restricting factor that limiting performance improves has: the spectral response of organic semiconductor material and solar radiation spectrum do not mate, the electrode collection effciency of the carrier mobility that organic semiconductor is relatively low and lower current carrier etc.In order to make polymer solar battery obtain actual application, the material of development of new increases substantially the top priority that its effciency of energy transfer is still this research field.
Porphyrin Molecule is the general name that is connected with a substituent class macrocylc compound at porphin ring, and porphines is the large ring delocalizedπelectron of the two dimensional structure conjugated system that is replaced by the Dan Shuanjian that four pyrrole rings and four methyne bridgings get up.The quantum yield of their charge transfer and energy transfer reaction is higher, has good electronics resiliency and photoelectric magnetic property, good hard and soft property and better thermostability and environmental stability.Therefore, the porphyrin organic semiconductor material is the up-and-coming material of a class, and its application in the photovoltaic field has obtained broad research.
Carbazole is the good hole mobile material of a class: on the one hand, because the pi-conjugated effect of p-, the N atom on the carbazole not shared electron is supplied with two keys, makes two key electron riches; On the other hand, the N atom of parent electricity absorbs electronics on two keys by inductive effect again, and wherein conjugative effect is greater than inductive effect, so carbazole has very strong cavity transmission ability, and this just makes it that very large potential using value is arranged aspect organic semiconductor material.
Thieno-[3,4-b] pyrazine is a kind of good two dimensional structure that has, and contains the body unit that is subjected to of a five-ring and six-ring skeleton, has intramolecular charge and shifts character and excellent electrochemical reduction character; Thieno-[3,4-b] pyrazine unit also has stronger modifiability, can utilize easy method to introduce electron-donating group and electron-accepting group, regulates its electrophilic performance.Therefore, it is often as be incorporated in the photoelectric material to regulate bandwidth and reduction potential by body unit, with thieno-[3,4-b] pyrazine is incorporated into the donor material with D-A structural unit that forms in the carbazolyl porphyrin unit to electronics, and has simultaneously high hole mobility and wide sunlight absorption spectrum ranges.
Yet the organic semiconductor material that contains the porphyrin of carbazole-thienopyrazine copolymerization does not still have document and patent report so far, and this has just limited their range of application greatly.
Summary of the invention
The object of the present invention is to provide a kind of carbazolyl porphyrin-thienopyrazine multipolymer that contains, this multipolymer can address the above problem.
The present invention also aims to provide a kind of preparation method who contains carbazolyl porphyrin-thienopyrazine multipolymer.
The present invention also aims to provide and contain carbazolyl porphyrin-thienopyrazine multipolymer at polymer solar battery, organic electroluminescent, organic field effect tube, organic optical storage, the application in the fields such as organic non-linear optical properties and organic laser material.
Carbazolyl porphyrin-thienopyrazine the multipolymer that contains involved in the present invention has following structure (I):
In the formula: n is the integer between 1-100, R
1, R
2Be identical or not identical hydrogen or C
1-C
32Alkyl.
The preparation method who contains carbazolyl porphyrin-thienopyrazine multipolymer that the present invention is designed, scheme is as follows:
5 of structural formula (A) is provided, 15-two bromo-10, two boric acid ester group thieno-s [3,4-b] pyrazine of 20-alkyl carbazole porphyrin and structural formula (B):
Under the oxygen-free environment that nitrogen and/or rare gas element form, with 5,15-, two bromo-10,20-alkyl carbazole porphyrin carries out the Suzuki coupling reaction with two boric acid ester group thieno-[3,4-b] pyrazines under the condition of catalyzer and organic solvent; Wherein, catalyzer can be organic palladium, as: Pd
2(dba)
3, Pd (OAc)
2, Pd (PPh
3)
4Or Pd (PPh
3)
2Cl
2Deng, can also for organic palladium and organophosphorus ligand (as, tricyclohexyl phosphine, P (o-Tol)
3) mixture; When described catalyzer was the mixture of organic palladium and organophosphor ligand, the mixed mol ratio of described organic palladium and organophosphorus ligand was 1: 2-20.1; The mole dosage of catalyzer is the 0.05%-30% of two boric acid ester group thieno-[3,4-b] pyrazines, 5,15-, two bromo-10, and 20-alkyl carbazole porphyrin is 1: 1.5～1.5: 1 with the consumption mol ratio of two boric acid ester group thieno-[3,4-b] pyrazines; Temperature of reaction is 50-120 ℃, and the reaction times is 12～72 hours.Described organic solvent is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene or the toluene etc., and the organic solvent capacity;
Suzuki coupling reaction formula is as follows:
A kind of carbazolyl porphyrin provided by the invention-thienopyrazine multipolymer, by introducing the thienopyrazine structural unit, because this structural unit has good two dimensional structure, the body unit that is subjected to that contains a five-ring and six-ring skeleton, and have intramolecular charge and shift character, therefore, the spectral bandwidth of material of the present invention has effectively been regulated in the existence of this thienopyrazine structural unit; In addition, also by introducing chain alkyl, improve the solubility property of material; Simultaneously, be conducive to film forming processing, enlarge them in the range of application in the fields such as polymer solar battery.Technique is simple in the material preparation method of the present invention, and reaction conditions is gentle, is easy to operate and control, and is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is with the structural representation of the multipolymer among the present invention as the organic solar batteries device of active coating.
Fig. 2 is with the structural representation of the multipolymer among the present invention as the organic electroluminescence device of luminescent layer.
Fig. 3 is with the structural representation of the multipolymer among the present invention as the organic field effect tube device of organic semiconductor layer.
Embodiment
Carbazolyl porphyrin-thienopyrazine the multipolymer that contains involved in the present invention has following structure (I):
In the formula: n is the integer between 1-100, R
1, R
2Be identical or not identical hydrogen or C
1-C
32Alkyl.
A kind of preparation method who contains carbazolyl porphyrin-thienopyrazine multipolymer comprises the steps:
5 of structural formula (A) is provided, 15-two bromo-10, two boric acid ester group thieno-s [3,4-b] pyrazine of 20-alkyl carbazole porphyrin and structural formula (B):
In the formula: n is the integer between 1-100, R
1, R
2Be identical or not identical hydrogen or C
1-C
32Alkyl.
In the oxygen-free environment (the present invention adopts nitrogen and/or rare gas element to form oxygen-free environment as shielding gas), under catalyzer and the organic solvent existence condition, with 5,15-two bromo-10,20-alkyl carbazole porphyrin and two boric acid ester group thieno-s [3,4-b] pyrazine carries out the Suzuki coupling reaction, makes the described solution that contains carbazolyl porphyrin-thienopyrazine multipolymer of structural formula (I); Wherein, the mole dosage of described catalyzer is the 0.05%-30% of two boric acid ester group thieno-[3,4-b] pyrazines; 5,15-, two bromo-10,20-alkyl carbazole porphyrin is 1: 1.5～1.5: 1 with the consumption mol ratio of two boric acid ester group thieno-[3,4-b] pyrazines; Organic solvent is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene or the toluene; Temperature of reaction is 50-120 ℃, and the reaction times is 12～72 hours;
Reaction formula is as follows:
Among the present invention, 2-bromo-9-alkyl carbazole is made under catalyzer/organic solvent condition by 2-bromine carbazole and bromine alkane, (reference: Macromolecules 2002,35,3474); 2-aldehyde-9-alkyl carbazole is made in n-Butyl Lithium/dimethyl formamide/Tetrahydrofuran System by 2-bromo-9-alkyl carbazole, (reference: Macromolecules 2006,39,456); Isosorbide-5-Nitrae-dipyrryl the methylbenzene is made under catalyst action by terephthalaldehyde and pyrroles, dipyrrylmethanes is made under catalyst action by formaldehyde and pyrroles, (reference: Tetrahedron 1994,39,11427).
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
Present embodiment discloses a kind of as 10 of organic semiconductor material, 20-two (9-octyl group carbazole) porphyrin thieno-[3,4-b] pyrazine multipolymer, and its structural formula is as follows:
In the formula: n is the integer between 1-100.
The preparation process of this multipolymer is as follows:
One, 5,7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) basic thieno-[3,4-b] pyrazine synthetic
Under the protection of nitrogen; in there-necked flask, add 5; 7-dibromo thiophene also [3; 4-b] pyrazine 8.8g (being 0.03mol); the tetrahydrofuran solvent that adds 200ml; under-78 ℃ of conditions again with syringe slowly implantation concentration be the n-Butyl Lithium 25.2mL (being 0.06mol) of 2.5M; after continuing stirring reaction 2h; under-78 ℃ of conditions, inject 2-isopropoxy-4,4,5 with syringe; 5-tetramethyl--1; 3,2-, two assorted oxygen pentaborane 13mL (being .06mol) are warming up to stir under the room temperature and spend the night.Add again saturated 30ml sodium chloride aqueous solution termination reaction, use subsequently chloroform extraction, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve and evaporate solvent; At last crude product is separated for leacheate carries out silica gel column chromatography with petrol ether/ethyl acetate (15/1, volume ratio), obtain product, productive rate 93%.
Elem.Anal.Calcd.For?C
18H
26B
2N
2O
4S：C，55.71％；H，6.75％；N，7.22％；S，8.26％；Found：C，55.79％；H，6.68％；N，7.24％；S，8.29％.GC-MS(EI-m/z)：388(M
+)
Two, 5,15-two (9-octyl group carbazole) porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing intermediate 2-aldehyde-9-octyl group carbazole 0.31g (being 1mmol) and dipyrrylmethanes 0.15g (being 1mmol), be dissolved in the 250ml methylene dichloride, pass into nitrogen 30min and remove oxygen; Syringe adds the 1ml propionic acid subsequently, then 20 ℃ of lower 24h that stir add DDQ (DDQ) 0.91g (being 4mmol), continue at room temperature to stir 30min, then add 1ml triethylamine cancellation reaction, concentrated solvent filters, and collects filtrate and is spin-dried for solvent, with methylene dichloride fast drip washing on silicagel column, be spin-dried for solvent, to product, productive rate is about 84% with ether/recrystallizing methanol.
Elem.Anal.Calcd.For?C
60H
60N
6：C，83.30％；H，6.99％；N，9.71％；Found：C，83.36％；H，6.91％；N，9.73％.GC-MS(EI-m/z)：865(M
+)
Three, 5,15-two bromo-10,20-two (9-octyl group carbazole) porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing 5,15-two (9-octyl group carbazole) porphyrin 0.17g (being 0.2mmol) and be dissolved in the 80ml chloroform, add the 1ml pyridine, reactant is dropped to 0 ℃, add N-bromo-succinimide 0.07g (being 0.4mmol), behind the stirring 72h, temperature of reaction is returned to room temperature, then continue to stir 4h, add 5ml acetone termination reaction, subsequently desolventizing, carry out recrystallization with ether/methyl alcohol and obtain product, productive rate 82%.
Elem.Anal.Calcd.For?C
60H
58Br
2N
6：C，70.45％；H，5.71％；N，8.22％；Found：C，70.38％；H，5.63％；N，8.26％.GC-MS(EI-m/z)：1022(M
+)
Four, 10,20-two (9-octyl group carbazole) porphyrin thieno-[3,4-b] pyrazine Synthesis of copolymer
Under nitrogen protection, add 5,7-two (4; 4; 5,5-tetramethyl--1,3; 2-two assorted oxygen pentaboranes) basic thieno-[3; 4-b] pyrazine 78mg (being 0.2mmol), 5,15-two bromo-10,20-two (9-octyl group carbazole) porphyrin 204mg (being 0.2mmol) and toluene solvant 80ml; vacuumize deoxygenation and be filled with nitrogen, then add the Pd (PPh of 5mg
3)
2Cl
2, be heated to 100 ℃ of reaction 56h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 250ml methyl alcohol.Suction filtration, methanol wash, drying.Then with the toluene dissolving, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone apparatus,Soxhlet's.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, productive rate 77%.
Molecular?weight(GPC，THF，R.I)：Mn＝42700，Mw/Mn＝2.88；)
Embodiment 2
Present embodiment discloses the multipolymer of a kind of 10-as organic semiconductor material (9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin thieno-[3,4-b] pyrazine, and its structural formula is as follows:
In the formula: n is the integer between 1-100.
The preparation process of this multipolymer is as follows:
One, 5,7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) basic thieno-[3,4-b] pyrazine synthetic
Its preparation sees embodiment 1 for details.
Two, 5-(9-methyl carbazole)-15-(9-dotriacontyl carbazole) porphyrin is synthetic
Put up the anhydrous and oxygen-free device, take by weighing intermediate 2-aldehyde-9-methyl carbazole (0.21g, 1mmol), 2-aldehyde-9-dotriacontyl carbazole 0.65g (being 1mmol), dipyrrylmethanes 0.30g (being 2mmol), be dissolved in the 250ml methylene dichloride, pass into nitrogen 30min, syringe adds trifluoroacetic acid 2ml, 100 ℃ of lower 1h that stir, then add DDQ (DDQ) 1.82g (being 8mmol), continue at room temperature to stir 30min, then add 2ml pyridine cancellation reaction, concentrated solvent, filter, collect filtrate and be spin-dried for solvent, with methylene dichloride fast drip washing on silicagel column, be spin-dried for solvent, to product, productive rate is about 73% with ether/recrystallizing methanol.
Elem.Anal.Calcd.For?C
77H
94N
6：C，83.80％；H，8.59％；N，7.62％；Found：C，83.89％；H，8.54％；N，7.57％.GC-MS(EI-m/z)：1102(M
+)
Three, 5,15-two bromo-10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin synthetic
Put up the anhydrous and oxygen-free device, taking by weighing 5-(9-methyl carbazole)-15-(9-dotriacontyl carbazole) porphyrin 0.22g (being 0.2mmol) is dissolved in the 80ml chloroform, add the 1ml pyridine, reactant is dropped to 0 ℃, add N-bromo-succinimide 0.07g (being 0.4mmol), after stirring 0.5h, temperature of reaction is warming up to 120 ℃, then after continuing to stir 1h, add 5ml acetone termination reaction, subsequently desolventizing is carried out recrystallization with ether/methyl alcohol and is obtained product, productive rate 83%.
Elem.Anal.Calcd.For?C
77H
92Br
2N
6：C，73.32％；H，7.35％；N，6.66％；Found：C，73.39％；7.28％；N，6.57％.GC-MS(EI-m/z)：1261(M
+)
Four, 10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin thieno-[3,4-b] pyrazine Synthesis of copolymer
Under nitrogen protection; add 5,7-two (4,4; 5; 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic thieno-[3; 4-b] pyrazine 78mg (being 0.2mmol), 5; 15-two bromo-10-(9-methyl carbazole)-20-(9-dotriacontyl carbazole) porphyrin 252mg (being 0.2mmol) and toluene solvant 80ml vacuumizes deoxygenation and is filled with nitrogen, then adds the Pd (PPh of 5mg
3)
2Cl
2, the Pd of 2.5mg (OAc)
2The Et of the tricyclohexyl phosphine of/6.5mg and 2ml concentration 20% (wt)
3NOH solution is heated to 120 ℃ of reaction 24h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 250ml methyl alcohol.Suction filtration, methanol wash, drying.Then with the toluene dissolving, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone apparatus,Soxhlet's.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, productive rate 73%.Molecular weight (GPC, THF, R.I): Mn=37600, Mw/Mn=3.29; )
Embodiment 3
Present embodiment discloses a kind of 10-carbazole-20-as organic semiconductor material (9-hexadecyl carbazole) porphyrin thieno-[3,4-b] pyrazine multipolymer, and its structural formula is as follows:
In the formula: n is the integer between 1-100.
The preparation process of this multipolymer is as follows:
One, 5,7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) basic thieno-[3,4-b] pyrazine synthetic
Its preparation sees embodiment 1. for details
Two, 5-carbazole-15-(9-hexadecyl carbazole) porphyrin is synthetic
Put up the anhydrous and oxygen-free device, take by weighing intermediate 2-aldehyde carbazole 0.20g (being 1mmol), 2 aldehyde-9-hexadecyl carbazole 0.42g (being 1mmol), dipyrrylmethanes 0.30g (being 2mmol), be dissolved in the 300ml methylene dichloride, pass into nitrogen 30min, syringe adds trifluoroacetic acid 2ml, stir 3h under the room temperature, then add DDQ (DDQ) 1.82g (being 8mmol), continue at room temperature to stir 30min, then add 2ml triethylamine cancellation reaction, concentrated solvent filters, and collects filtrate and is spin-dried for solvent, with methylene dichloride fast drip washing on silicagel column, be spin-dried for solvent, to product, productive rate is about 88% with ether/recrystallizing methanol.
Elem.Anal.Calcd.For?C
60H
60N
6：C，83.30％；H，6.99％；N，9.71％；Found：C，83.38％；6.94％；N，9.68％.GC-MS(EI-m/z)：865(M
+)
Three, 5,15-two bromo-10-carbazole-20-(9-hexadecyl carbazole) porphyrin synthetic
Put up the anhydrous and oxygen-free device, take by weighing 5-carbazole-15-(9-hexadecyl carbazole) porphyrin 0.17g (being 0.2mmol) and be dissolved in the 80ml chloroform, add the 1ml pyridine, reactant is dropped to 0 ℃, add N-bromo-succinimide 0.07g (being 0.4mmol), after stirring 0.5h, temperature of reaction is warming up to 30 ℃, then continues to stir 48h, add 5ml acetone termination reaction, subsequently desolventizing is carried out recrystallization with ether/methyl alcohol and is obtained product, productive rate 78%.
Elem.Anal.Calcd.For?C
60H
58Br
2N
6：C，70.45％；H，5.71％；N，8.22％；Found：C，70.55％；H，5.66％；8.25％.GC-MS(EI-m/z)：1023(M
+)
Four, 10-carbazole-20-(9-hexadecyl carbazole) porphyrin thieno-[3,4-b] pyrazine Synthesis of copolymer
Under nitrogen protection; add 5,7-two (4,4; 5; 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic thieno-[3; 4-b] pyrazine 78mg (being 0.2mmol), 5; 15-two bromo-10-carbazole-20-(9-hexadecyl carbazole) porphyrin 205mg (being 0.2mmol) and toluene solvant 100ml vacuumize deoxygenation and are filled with nitrogen, then add the Pd (PPh of 8mg
3)
4, be heated to 50 ℃ of reaction 72h.Be cooled to after the room temperature mixed solution is added drop-wise to and carry out sedimentation in the 300ml methyl alcohol.Suction filtration, methanol wash, drying.Then with the toluene dissolving, join in the aqueous solution of Thiocarb, then mixed solution is heated to 80 ℃ of stirrings and spends the night.With the column chromatography of organic phase by aluminum oxide, chlorobenzene drip washing.Organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, the gained solid extracted three days with the acetone Soxhlet.The methyl alcohol sedimentation, suction filtration.Taking out under the vacuum pump spends the night obtains product, productive rate 80%.
Molecular?weight(GPC，THF，R.I)：Mn＝39300，Mw/Mn＝3.48；)。
Following examples are to contain carbazolyl porphyrin-thienopyrazine multipolymer at polymer solar battery, organic electroluminescence device, organic field effect tube, organic optical storage, the application in the fields such as organic non-linear optical properties and organic laser material.
Embodiment 4
A kind of solar cell device, its structure such as Fig. 1.Substrate in the present embodiment adopts ito glass, and glass is as substrate, and ITO is as conductive layer.
The structure of this organic solar batteries device is: glass/ITO/PEDOT:PSS/ active coating/Al; Wherein, the material of active coating is mixture, comprises with [6,6] phenyl-C
61-methyl-butyrate is the electron donor material of material and to contain carbazolyl porphyrin-thienopyrazine multipolymer as the electron acceptor material of material; ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and PEDOT is poly-(3,4-Ethylenedioxy Thiophene), and PSS is poly-(styrene sulfonic acid).
This organic solar batteries device gets preparation process:
Tin indium oxide (ITO) in that surface deposition one deck square resistance of glass substrate is 10-20 Ω/mouth forms the conductive layer as anode;
Ito glass process ultrasonic cleaning, and with after oxygen-Plasma processing, be coated with the PEDOT:PSS layer that last layer plays modification on the ITO surface;
Adopt spin coating technique to apply one deck active coating at described poly-(3,4-Ethylenedioxy Thiophene): PSS on (styrene sulfonic acid) layer for gathering, the material of this active coating is mixture, comprises with [6,6] phenyl-C
61-methyl-butyrate is the electron donor material of material and to contain carbazolyl porphyrin-thienopyrazine multipolymer as the electron acceptor material of material
At the surface vacuum evaporation metal aluminium of described active coating, form the metal aluminium lamination as negative electrode, obtain described organic solar batteries device.Wherein, the thickness of metal aluminium lamination is respectively 170nm, 30nm, 130nm, 60nm.
Embodiment 5
A kind of organic electroluminescence device, its structure is as shown in Figure 2; Substrate in the present embodiment adopts ito glass, and glass is as substrate, and ITO is as conductive layer.
The structure of this organic electroluminescence device is: glass/ITO/ luminescent layer/LiF/Al; Wherein: luminescent layer take of the present invention as carbazolyl porphyrin-thienopyrazine multipolymer as material.
The preparation process of this organic electroluminescence device is:
Tin indium oxide (ITO) in that surface deposition one deck square resistance of glass substrate is 10-20 Ω/mouth forms the conductive layer as anode;
Prepare one deck take the carbazolyl porphyrin-thienopyrazine multipolymer that contains of the present invention as the luminescent layer of material by spin coating technique on the ITO surface;
Vacuum evaporation LiF on luminescent layer is as buffer layer;
Vacuum evaporation metallic aluminium on described luminescent layer forms the metal aluminium lamination as negative electrode, obtains described organic electroluminescence device.
Embodiment 6
A kind of organic field effect tube, its structure is as shown in Figure 3; Substrate in the present embodiment adopts doped silicon wafer (Si) as substrate.
The structure of this organic field effect tube is: the SiO that Si/450nm is thick
2Insulation layer/for modifying SiO
2Octadecyl trichlorosilane alkane (OTS)/source electrode (S) and the drain electrode (D) of organic semiconductor layer/LiF/ take gold as material; Wherein, organic semiconductor layer is take the carbazolyl porphyrin-thienopyrazine multipolymer that contains of the present invention as material; Source electrode (S) and drain electrode (D) also can adopt copper material.
This organic field effect tube gets preparation process:
At first, apply one deck SiO on a surface cleaning doped silicon wafer later
2Insulation layer; Secondly, at described SiO
2Apply the octadecyl trichlorosilane alkane layer that one deck plays modification on the insulation layer; Then, on described octadecyl trichlorosilane alkane layer spin coating one deck take the carbazolyl porphyrin-thienopyrazine multipolymer that contains of the present invention as the organic semiconductor layer of material; At last, be arranged at intervals with source electrode (S) and drain electrode (D) take gold as material at described organic semiconductor layer, obtain described organic field effect tube.
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, scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. one kind contains carbazolyl porphyrin-thienopyrazine multipolymer, it is characterized in that, has following structural formula (I):
In the formula: n is the integer between 1-100, R
1, R
2Be identical or not identical hydrogen or C
1-C
32Alkyl.
2. a preparation method who contains carbazolyl porphyrin-thienopyrazine multipolymer is characterized in that described preparation method comprises the steps:
5 of structural formula (A) is provided, 15-two bromo-10, two boric acid ester group thieno-s [3,4-b] pyrazine of 20-alkyl carbazole porphyrin and structural formula (B):
In the oxygen-free environment, under catalyzer and the organic solvent existence condition, with 5,15-two bromo-10,20-alkyl carbazole porphyrin carries out the Suzuki coupling reaction with two boric acid ester group thieno-[3,4-b] pyrazines, makes the described solution that contains carbazolyl porphyrin-thienopyrazine multipolymer of structural formula (I);
Reaction formula is as follows:
In the formula: n is the integer between 1-100, R
1, R
2Be identical or not identical hydrogen or C
1-C
32Alkyl.
3. preparation method according to claim 2 is characterized in that, in the Suzuki coupling reaction, the mole dosage of described catalyzer is the 0.05%-30% of two boric acid ester group thieno-[3,4-b] pyrazines; Described 5,15-two bromo-10,20-alkyl carbazole porphyrin is 1:1.5 ~ 1.5:1 with the consumption mol ratio of two boric acid ester group thieno-[3,4-b] pyrazines; Temperature of reaction is 50-120 ℃, and the reaction times is 12 ~ 72 hours.
4. according to claim 2 or 3 described preparation methods, it is characterized in that described catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand;
Described organic palladium is Pd
2(dba)
3, Pd (PPh
3)
4, Pd (OAc)
2, or Pd (PPh
3)
2Cl
2
Described organophosphor ligand is P (o-Tol)
3Or tricyclohexyl phosphine.
5. preparation method according to claim 4 is characterized in that, the mixed mol ratio of described organic palladium and organophosphorus ligand is 1:2-20.
6. preparation method according to claim 2 is characterized in that, described organic solvent is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene or the toluene; Described oxygen-free environment is made of nitrogen and/or rare gas element.
7. preparation method according to claim 2 is characterized in that, the Suzuki coupling reaction also comprises the described carbazolyl porphyrin-thienopyrazine multipolymer that contains is carried out purification step after finishing:
Described copolymer solution is added drop-wise in the methyl alcohol, carries out sedimentation and process, suction filtration then, methanol wash, drying must contain assorted copolymer colloid; With the toluene dissolving, get the toluene solution of multipolymer subsequently;
This toluene solution is joined in the aqueous solution of Thiocarb, 80-100 ℃ of heated and stirred mixed solution, with the column chromatography of mixed solution by aluminum oxide, isolate multipolymer, then chlorobenzene drip washing, organic solvent is removed in subsequently decompression, extracts multipolymer with the acetone Soxhlet at last, obtains described copolymer solids.
8. organic solar batteries device, comprise substrate, be deposited on one of substrate lip-deep, as the conductive layer of anode, be coated in and play poly-(3 of modification on the conductive layer, the 4-Ethylenedioxy Thiophene): poly-(styrene sulfonic acid) layer, be coated in poly-(3,4-Ethylenedioxy Thiophene): the active coating on poly-(styrene sulfonic acid) layer surface, and be arranged on the active coating surface, as the metal aluminium lamination of negative electrode; It is characterized in that the material of described active coating is mixture, comprise with [6,6] phenyl-C
61-methyl-butyrate is the electron donor material of material and to contain carbazolyl porphyrin-thienopyrazine multipolymer as the electron acceptor material of material, and this multipolymer has following structural formula (I):
In the formula: n is the integer between 1-100, R
1, R
2Be identical or not identical hydrogen or C
1-C
32Alkyl.
9. organic electroluminescence device, comprise substrate, be deposited on of substrate lip-deep, as the conductive layer of anode, be coated in the luminescent layer on the conductive layer, be coated in the buffer layer take LiF as material on the luminescent layer, and be arranged on the buffer layer, as the metal aluminium lamination of negative electrode, it is characterized in that, described luminescent layer is to contain carbazolyl porphyrin-thienopyrazine multipolymer as material, and this multipolymer has following structural formula (I):
In the formula: n is the integer between 1-100, R
1, R
2Be identical or not identical hydrogen or C
1-C
32Alkyl.
10. an organic field effect tube device comprises doped silicon wafer, SiO
2Insulation layer is used for modifying SiO
2Octadecyl trichlorosilane alkane layer, be coated in the organic semiconductor layer on the octadecyl trichlorosilane alkane layer, be disposed on source electrode and drain electrode on the organic semiconductor layer, it is characterized in that, described organic semiconductor layer is to contain carbazolyl porphyrin-thienopyrazine multipolymer as material, and this multipolymer has following structural formula (I):
In the formula: n is the integer between 1-100, R
1, R
2Be identical or not identical hydrogen or C
1-C
32Alkyl.
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| GB2430679A (en) * | 2005-09-28 | 2007-04-04 | Riso Nat Lab | Photovoltaic polymer |
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