CN102295757A - 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
- Publication number
- CN102295757A CN102295757A CN2010102115340A CN201010211534A CN102295757A CN 102295757 A CN102295757 A CN 102295757A CN 2010102115340 A CN2010102115340 A CN 2010102115340A CN 201010211534 A CN201010211534 A CN 201010211534A CN 102295757 A CN102295757 A CN 102295757A
- Authority
- CN
- China
- Prior art keywords
- multipolymer
- thieno
- porphyrin
- pyrazine
- carbazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 *Cc([s]c(C(C(C=C1)=NC1=C1c2ccc(c3ccccc3[n]3*)c3c2)=C(C=C2)NC2=C([C@]2C=C3N(*)c4ccccc4C3=CC2)C(C=C2)=NC2=C(*(*)*)[C@@]2NC1=CC2)c1N)c1N Chemical compound *Cc([s]c(C(C(C=C1)=NC1=C1c2ccc(c3ccccc3[n]3*)c3c2)=C(C=C2)NC2=C([C@]2C=C3N(*)c4ccccc4C3=CC2)C(C=C2)=NC2=C(*(*)*)[C@@]2NC1=CC2)c1N)c1N 0.000 description 1
- ZEDUXLBKSLFGQC-ZKGSUICBSA-N C[n]1c2cc(/C(/C(C=C3)=N/C3=C(/C[Br](C)/C(/C(C=C3)=N/C3=C(\c3ccc(/C(/[BrH]C)=C4\N=C5C=C4)[nH]3)/c3ccc(c(cccc4)c4[nH]4)c4c3)=C(\C=C3)/N/C3=C5/c(cc3)cc4c3c(cccc3)c3[n]4C)\c3ccc4[nH]3)=C(\C=C3)/N/C3=C\C(C=C3)=N/C3=C4/c3ccc(c4ccccc4[nH]4)c4c3)ccc2c2ccccc12 Chemical compound C[n]1c2cc(/C(/C(C=C3)=N/C3=C(/C[Br](C)/C(/C(C=C3)=N/C3=C(\c3ccc(/C(/[BrH]C)=C4\N=C5C=C4)[nH]3)/c3ccc(c(cccc4)c4[nH]4)c4c3)=C(\C=C3)/N/C3=C5/c(cc3)cc4c3c(cccc3)c3[n]4C)\c3ccc4[nH]3)=C(\C=C3)/N/C3=C\C(C=C3)=N/C3=C4/c3ccc(c4ccccc4[nH]4)c4c3)ccc2c2ccccc12 ZEDUXLBKSLFGQC-ZKGSUICBSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 a kind of carbazole porphyrin-thieno-pyrazine multipolymer that contains more specifically.
The invention still further relates to the preparation method and the application thereof that contain carbazole porphyrin-thieno-pyrazine multipolymer.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is the research focus and the difficult point in photovoltaic field always.The silicon wafer battery that is used for ground at present is restricted its application owing to complex manufacturing, cost height.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 good advantages such as photovoltaic effect to receive much concern.Go up report conjugated polymers and C from N.S.Sariciftci in 1992 etc. at SCIENCE (N.S Sariciftci, L.Smilowitz, A.J.Heeger, etal.Science, 1992,258,1474)
60Between photoinduction transfer transport phenomenon after, people have dropped into big 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 match, the electrode collection effciency of 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.
The porphyrin molecule is the general name that is connected with a substituent class macrocylc compound on porphin ring, and porphines is by four pyrrole rings and four the big ring delocalized of Dan Shuanjian alternative two dimensional structure conjugated systems that the methyne bridging gets up.The quantum yield of their charge transfer and energy transfer reaction is higher, has good electron resiliency and photoelectric magnetic property, good hard and soft property and better thermostability and environmental stability.Therefore, porphyrin class 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 big 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 carbazole porphyrin unit to electronics, and has high hole mobility and wide sunlight absorption spectrum ranges simultaneously.
Yet the organic semiconductor material that contains the porphyrin-thieno-pyrazine copolymerization of carbazole 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 carbazole porphyrin-thieno-pyrazine multipolymer that contains, this multipolymer can address the above problem.
The present invention also aims to provide a kind of preparation method who contains carbazole porphyrin-thieno-pyrazine multipolymer.
The present invention also aims to provide and contain carbazole porphyrin-thieno-pyrazine multipolymer at polymer solar battery, organic electroluminescent, organic field effect tube, organic optical storage, Application for Field such as organic non-linear optical properties and organic laser material.
Carbazole porphyrin-thieno-pyrazine 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 hydrogen identical or inequality or C
1-C
32Alkyl.
The preparation method who contains carbazole porphyrin-thieno-pyrazine 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 are formed, 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, and 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.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 carbazole porphyrin provided by the invention-thieno-pyrazine multipolymer, by introducing thieno-pyrazine 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 thieno-pyrazine structural unit; In addition, also, improve the solubility property of material by introducing chain alkyl; Simultaneously, help film forming processing, enlarge their ranges of application in fields such as polymer solar batteries.Technology is simple in the material preparation method of the present invention, and the reaction conditions gentleness 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
Carbazole porphyrin-thieno-pyrazine 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 hydrogen identical or inequality or C
1-C
32Alkyl.
A kind of preparation method who contains carbazole porphyrin-thieno-pyrazine 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 hydrogen identical or inequality 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 carbazole porphyrin-thieno-pyrazine 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 (THF) system by 2-bromo-9-alkyl carbazole, (reference: Macromolecules 2006,39,456); 1,4-is made under catalyst action by terephthalaldehyde and pyrroles the dipyrryl methylbenzene, and two pyrroles's methane are 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 protection of nitrogen gas, add to 5 7-dibromo thiophene also [3 in the there-necked flask; 4-b] pyrazine 8.8g (being 0.03mol), add the tetrahydrofuran solvent of 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 saturated 30ml sodium chloride aqueous solution termination reaction again, use chloroform extraction subsequently, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve and steam 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 two pyrroles's methane 0.15g (being 1mmol), be dissolved in the 250ml methylene dichloride, feed nitrogen 30min and remove oxygen; Syringe adds the 1ml propionic acid subsequently, 20 ℃ are stirred 24h down, add DDQ (DDQ) 0.91g (being 4mmol) then, continue at room temperature to stir 30min, add 1ml triethylamine cancellation reaction then, concentrated solvent filters, and collects filtrate and is spin-dried for solvent, with methylene dichloride drip washing fast 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) is 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, continue to stir 4h then, add 5ml acetone termination reaction, remove subsequently and desolvate, 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 multipolymer synthetic
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 charge into nitrogen, add the Pd (PPh of 5mg then
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.With the toluene dissolving, join in the aqueous solution of Thiocarb then, 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), two pyrroles's methane 0.30g (being 2mmol), be dissolved in the 250ml methylene dichloride, feed nitrogen 30min, syringe adds trifluoroacetic acid 2ml, and 100 ℃ are stirred 1h down, add DDQ (DDQ) 1.82g (being 8mmol) then, continue at room temperature to stir 30min, add 2ml pyridine cancellation reaction then, concentrated solvent, filter, collect filtrate and be spin-dried for solvent,, be spin-dried for solvent with methylene dichloride drip washing fast on silicagel column, 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, take by weighing 5-(9-methyl carbazole)-15-(9-dotriacontyl carbazole) porphyrin 0.22g (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 120 ℃, after continuing then to stir 1h, add 5ml acetone termination reaction, remove subsequently and desolvate, carry out recrystallization with ether/methyl alcohol and obtain 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 multipolymer is synthetic
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 charges into nitrogen, adds the Pd (PPh of 5mg then
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.With the toluene dissolving, join in the aqueous solution of Thiocarb then, 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, and 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), two pyrroles's methane 0.30g (being 2mmol), be dissolved in the 300ml methylene dichloride, feed nitrogen 30min, syringe adds trifluoroacetic acid 2ml, stir 3h under the room temperature, add DDQ (DDQ) 1.82g (being 8mmol) then, continue at room temperature to stir 30min, add 2ml triethylamine cancellation reaction then, concentrated solvent filters, and collects filtrate and is spin-dried for solvent, with methylene dichloride drip washing fast 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 ℃, continues to stir 48h then, add 5ml acetone termination reaction, remove subsequently and desolvate, carry out recrystallization with ether/methyl alcohol and obtain 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 multipolymer is synthetic
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 charge into nitrogen, add the Pd (PPh of 8mg then
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.With the toluene dissolving, join in the aqueous solution of Thiocarb then, 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 carbazole porphyrin-thieno-pyrazine multipolymer at polymer solar battery, organic electroluminescence device, organic field effect tube, organic optical storage, Application for Field 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 a mixture, comprises with [6,6] phenyl-C
61-methyl-butyrate is the electron donor material of material and is the electron acceptor material of material to contain carbazole porphyrin-thieno-pyrazine multipolymer; ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and PEDOT is poly-(3, the 4-Ethylenedioxy Thiophene), and PSS is poly-(styrene sulfonic acid).
This organic solar batteries device gets preparation process:
At the tin indium oxide (ITO) that surface deposition one deck square resistance of glass substrate is 10-20 Ω/mouth, form as the anodic conductive layer;
Ito glass process ultrasonic cleaning, and, be coated with the PEDOT:PSS layer that last layer plays modification on the ITO surface with after oxygen-Plasma processing;
Adopt spin coating technique to apply one deck active coating at described poly-(3, the 4-Ethylenedioxy Thiophene): PSS on (styrene sulfonic acid) layer for gathering, the material of this active coating is a mixture, comprises with [6,6] phenyl-C
61-methyl-butyrate is the electron donor material of material and is the electron acceptor material of material to contain carbazole porphyrin-thieno-pyrazine multipolymer
At the surface vacuum evaporation metal aluminium of described active coating, form 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 is that carbazole porphyrin-thieno-pyrazine multipolymer is a material with of the present invention.
The preparation process of this organic electroluminescence device is:
At the tin indium oxide (ITO) that surface deposition one deck square resistance of glass substrate is 10-20 Ω/mouth, form as the anodic conductive layer;
To contain carbazole porphyrin-thieno-pyrazine multipolymer be the luminescent layer of material with of the present invention at ITO surface preparation one deck by spin coating technique;
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/be used to modify SiO
2Octadecyl trichlorosilane (OTS)/organic semiconductor layer/LiF/ be the source electrode (S) and the drain electrode (D) of material with the gold; Wherein, to contain carbazole porphyrin-thieno-pyrazine multipolymer be material to organic semiconductor layer with of the present invention; Source electrode (S) and drain electrode (D) also can adopt copper material.
This organic field effect tube gets preparation process:
At first, on a surface cleaning doped silicon wafer, apply one deck SiO later
2Insulation layer; Secondly, at described SiO
2Apply the octadecyl trichlorosilane layer that one deck plays modification on the insulation layer; Then, on described octadecyl trichlorosilane layer spin coating one deck to contain carbazole porphyrin-thieno-pyrazine multipolymer be the organic semiconductor layer of material with of the present invention; At last, being arranged at intervals with the gold on described organic semiconductor layer is the source electrode (S) and the drain electrode (D) of material, obtains described organic field effect tube.
Should be understood that above-mentioned statement at 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 carbazole porphyrin-thieno-pyrazine multipolymer, it is characterized in that having following structural formula (I):
In the formula: n is the integer between 1-100, R
1, R
2Be hydrogen identical or inequality or C
1-C
32Alkyl.
2. a preparation method who contains carbazole porphyrin-thieno-pyrazine 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 formula: n is the integer between 1-100, R
1, R
2Be hydrogen identical or inequality or C
1-C
32Alkyl.
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 carbazole porphyrin-thieno-pyrazine multipolymer of structural formula (I);
Reaction formula is as follows:
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 carbazole porphyrin-thieno-pyrazine 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 handle, 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, chlorobenzene drip washing then, organic solvent is removed in decompression subsequently, 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 anodic conductive layer, 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, the 4-Ethylenedioxy Thiophene): the active coating of poly-(styrene sulfonic acid) laminar 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 a mixture, comprise with [6,6] phenyl-C
61-methyl-butyrate is the electron donor material of material and is the electron acceptor material of material to contain carbazole porphyrin-thieno-pyrazine multipolymer that this multipolymer has following structural formula (I):
In the formula: n is the integer between 1-100, R
1, R
2Be hydrogen identical or inequality or C
1-C
32Alkyl.
9. organic electroluminescence device, comprise substrate, be deposited on of substrate lip-deep, as the anodic conductive layer, be coated in the luminescent layer on the conductive layer, being coated on the luminescent layer is the buffer layer of material with LiF, and be arranged on the buffer layer, as the metal aluminium lamination of negative electrode, it is characterized in that, described luminescent layer is a material to contain carbazole porphyrin-thieno-pyrazine multipolymer, and this multipolymer has following structural formula (I):
In the formula: n is the integer between 1-100, R
1, R
2Be hydrogen identical or inequality or C
1-C
32Alkyl.
10. an organic field effect tube device comprises doped silicon wafer, SiO
2Insulation layer is used to modify SiO
2Octadecyl trichlorosilane layer, be coated in the organic semiconductor layer on the octadecyl trichlorosilane layer, be disposed on source electrode and drain electrode on the organic semiconductor layer, it is characterized in that, described organic semiconductor layer is a material to contain carbazole porphyrin-thieno-pyrazine multipolymer, and this multipolymer has following structural formula (I):
In the formula: n is the integer between 1-100, R
1, R
2Be hydrogen identical or inequality or C
1-C
32Alkyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010211534 CN102295757B (en) | 2010-06-25 | 2010-06-25 | Carbazolyl porphyrin-thienopyrazine-containing copolymer and preparation method as well as application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010211534 CN102295757B (en) | 2010-06-25 | 2010-06-25 | Carbazolyl porphyrin-thienopyrazine-containing copolymer and preparation method as well as application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102295757A true CN102295757A (en) | 2011-12-28 |
| CN102295757B CN102295757B (en) | 2013-04-17 |
Family
ID=45356449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010211534 Expired - Fee Related CN102295757B (en) | 2010-06-25 | 2010-06-25 | Carbazolyl porphyrin-thienopyrazine-containing copolymer and preparation method as well as application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102295757B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860033A (en) * | 2016-04-12 | 2016-08-17 | 南京林业大学 | Polythiophene with side chain containing hydrophilic group, and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887033A (en) * | 2003-10-31 | 2006-12-27 | 日产化学工业株式会社 | Charge-transporting organic material containing compound having 1,4-dithiin ring |
| GB2430679A (en) * | 2005-09-28 | 2007-04-04 | Riso Nat Lab | Photovoltaic polymer |
-
2010
- 2010-06-25 CN CN 201010211534 patent/CN102295757B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887033A (en) * | 2003-10-31 | 2006-12-27 | 日产化学工业株式会社 | Charge-transporting organic material containing compound having 1,4-dithiin ring |
| GB2430679A (en) * | 2005-09-28 | 2007-04-04 | Riso Nat Lab | Photovoltaic polymer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105860033A (en) * | 2016-04-12 | 2016-08-17 | 南京林业大学 | Polythiophene with side chain containing hydrophilic group, and preparation method thereof |
| CN105860033B (en) * | 2016-04-12 | 2018-01-05 | 南京林业大学 | Side chain contains polythiophene of hydrophilic radical and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102295757B (en) | 2013-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102906151B (en) | Conjugated polymer based on benzodithiophene and thienopyrazine, preparation method and uses thereof | |
| CN102344549B (en) | Porphyrin-pyrrolopyrrole copolymer containing carbazole, preparation method thereof and application thereof | |
| JP5546070B2 (en) | Copolymer containing fluorenylporphyrin-anthracene, process for producing the same and application thereof | |
| CN102295756B (en) | Carbazole porphyrin-thienothiadiazole copolymer as well as preparation method and application thereof | |
| CN102344553B (en) | Naphthalenetetracarboxylic acid diimide organic semiconductor material, preparation process thereof and application thereof | |
| CN102770476B (en) | Porphyrin copolymer containing quinoxaline unit, preparation method and uses thereof | |
| CN102329415B (en) | Porphyrin-quinoxaline copolymer containing carbazole, preparation method thereof and application thereof | |
| CN102453229B (en) | Metalloporphyrin-thienopyrazine organic semiconductor material, preparation method thereof and application thereof | |
| CN102417584B (en) | Metal porphyrin-anthracene organic semiconductor material as well as preparation method and application thereof | |
| CN102295757B (en) | Carbazolyl porphyrin-thienopyrazine-containing copolymer and preparation method as well as application thereof | |
| CN102134307B (en) | Perylene diimide-fluorene-thiophene and (3, 4-b) pyrazine conjugated polymer and preparation method and application thereof | |
| CN102329416B (en) | Porphyrin-diazosulfide copolymer containing carbazole, preparation method and application thereof | |
| CN102268128B (en) | Porphyrin copolymer containing thienophenazine unit as well as preparation method and application thereof | |
| CN102295750B (en) | Carbazole porphyrin-paranaphthalene copolymer and preparation method and application thereof | |
| CN102206330B (en) | Bi-thiophene silole-containing conjugated polymer and preparation method and application thereof | |
| CN102329417B (en) | Copolymer containing carbazole porphyrin-benzene and preparation method and application thereof | |
| CN102453233B (en) | Organic semiconductor material containing metalloporphyrin-triphenylamine and preparation method and application thereof | |
| CN102417586B (en) | Metal porphyrin-diazosulfide organic semiconductor material as well as preparation method and application thereof | |
| CN102453234B (en) | Metalloporphyrin-thienothiadiazole organic semiconductor material and preparation method and application thereof | |
| CN102344551B (en) | Organic semiconductor material containing naphthalene tetracarboxylic acid diimide, preparation method and application thereof | |
| CN102311538B (en) | Copolymer material containing carbazole porphyrin-triphenylamine and preparation method and application thereof | |
| CN102276800A (en) | Triphenylamine unit porphyrin copolymer as well as preparation method and application thereof | |
| CN102453232B (en) | Metalloporphyrin-pyrrolopyrrole organic semiconductor material and preparation method and application thereof | |
| CN102443141B (en) | Metalloporphyrin-quinoxaline organic semiconductor material and preparation method and application thereof | |
| CN115594828A (en) | Halogenated cyclopentadithiophene polymer, preparation method thereof and application thereof in photovoltaic devices |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130417 Termination date: 20190625 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |