CN102532492B - Crosslinking thiopheno[3,4-b] thiophene conjugated polymer and preparation method and application thereof - Google Patents
Crosslinking thiopheno[3,4-b] thiophene conjugated polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a crosslinking thiopheno[3,4-b] thiophene conjugated polymer and a preparation method and application thereof. The constitutional formula of the conjugated polymer is shown in a formula I, wherein R1 is a functional group capable of conducting crosslink under the condition that ultraviolet illumination, heating or initiators exist, R2 is a functional group capable of conducting crosslink under the condition that ultraviolet illumination, heating or initiators exist or a substituent group which is different from R1 and is not crosslinked, Ar1 and Ar2 are units which are identical or different and have conjugated characteristics, X1 and X2 are both selected from the following groups: H, F, Cl, Br, cyan and ester groups, a/(a+b) is any value from 0 to 1, and the a/(a+b) is not zero, n represents repeated number of main polymer chain units, and the value of n is a natural number equal to and larger than 4. The polymer has narrower band gaps, improves anti-solvent performance by crosslinking and has wide application prospect in photoelectric function devices, especially the field of polymer solar batteries.
Description
Technical field
The present invention relates to a class crosslinkable thieno-[3,4-b] thiophene conjugated polymer and preparation method thereof and application.
Background technology
Polymer solar battery is because it is cheap, lightweight, be easy to the advantages such as the preparation realizing large area flexible device; the broad interest of investigators is caused in today that problem of energy crisis is increasingly sharpened; and under the effort of numerous researcher; high efficiency polymer materials constantly occurs, highest energy transformation efficiency reaches 7-8%.(1)Chen，H.Y.；Hou，J.H.；Zhang，S.Q.；Liang，Y.Y.；Yang，G.W.；Yang，Y.；Yu，L.P.；Wu，Y.；Li，G.Nature photonics.2009，3，649；(2)Samuel C.Price；Andrew C.Stuart；Yang.L.Q.；Zhou.H.X.；You.W.JACS.2011，133，4625。(3) Lijun Huo, Shaoqing Zhang, Xia Guo, Feng Xu, Yongfang Li, and Jianhui Hou Angew.Chem.Int.Ed.2011,50,9697-9702; (4) Samuel C.Price, Andrew C.Stuart, Liqiang Yang, Huaxing Zhou, Wei You, J.Am.Chem.Soc.2011,133,4625-4631; (5) Ta-Ya Chu, Jianping Lu, Serge Beaupre, Yanguang Zhang, Jean-Remi Pouliot, Salem Wakim, Jiayun Zhou, Mario Leclerc, Zhao Li, Jianfu Ding, Ye Tao, J.Am.Chem.Soc.2011,133,4250-4253; (6) Yongye Liang, Zheng Xu, Jiangbin Xia, Szu-Ting Tsai, Yue Wu, Gang Li, Claire Ray, Luping Yu, Adv.Mater.2010,22, E135-E138; (7) Zhicai He, Chengmei Zhong, Xun Huang, Wai-Yeung Wong, Hongbin Wu, Liwei Chen, Shijian Su, Yong Cao, DOI:10.1002/adma.201103006; (8) Ming-Shin Su, Chih-Yin Kuo, Mao-Chuan Yuan, U-Ser Jeng, Chun-Jen Su, Kung-Hwa Wei Adv.Mater.2011,23,3315-3319; (9) Chad M.Amb, Song Chen, Kenneth R.Graham, Jegadesan Subbiah, Cephas E.Small, Franky So, John R.Reynolds, J.Am.Chem.Soc.2011,133,10062-10065; (10) Huaxing Zhou, Liqiang Yang, Andrew C.Stuart, Samuel C.Price, Shubin Liu, Wei You, Angew.Chem.Int.Ed.2011,50,2995-2998.) organic solar batteries can the prospect of commercial applications to allow people see.
Although the material of above-mentioned report has higher effciency of energy transfer, there are two class problems in these materials.One is that institute's film forming does not have good solubility-resistence, existing conjugated polymers donor material and soccerballene and derivative acceptor material thereof are all soluble in the organic solvent such as orthodichlorobenzene, trichloromethane, when preparing multilayer film, lower membrane can dissolve by the solvent of upper solution, therefore cannot prepare multilayered structure device.Two is that the thermal stability of device is poor, major cause is that in blend film, polymkeric substance and soccerballene and derivative thereof tend to each self-separation, therefore formed nanometer micro phase separation structure is heat-labile, and it by change gradually in the operating process of device, thus causes the reduction of device performance.
Summary of the invention
An object of the present invention is to provide a class and contains conjugated polymers of thieno-[3, the 4-b] thiophene of band crosslinked group and preparation method thereof.
The conjugated polymers of thieno-[3, the 4-b] thiophene containing band crosslinked group provided by the present invention, its structural formula is such as formula shown in I:
(formula I)
In formula I, R
1in ultraviolet lighting or heating or crosslinkable functional group (functional group is atom or the atomic group of the chemical property determining organic compound) under adding initiator, R
2can be and R
1identical functional group, also can be and R
1different not crosslinkable substituting groups;
Ar
1, Ar
2it is identical or the not identical unit with conjugate character;
X
1, X
2can be any one in identical or not identical following radicals: H, F, Cl, Br, cyano group and ester group;
A/ (a+b) is the arbitrary value of 0-1 and a/ (a+b) is not 0;
The repetition number of n representation polymer backbone units, its numerical value be more than or equal to 4 natural number.
Wherein, described crosslinkable functional group is selected from any one in following structure:
K is the arbitrary natural number between 0-16.
Described not crosslinkable substituting group is C
1-C
18alkyl, C
1-C
18alkoxyl group or C
1-C
18sulfuryl.
The described unit with conjugate character is replaced any one in following radicals by alkyl or alkoxyl group: benzene, thiophene, naphthalene, anthracene, fluorenes, triphenylamine, thiodiphenylamine, pyrroles, thiazole, pyridine, dipyridyl, quinoline, furans, biphenyl, thieno-[3, 2-b] thiophene, thieno-[3, 4-b] thiophene, thieno-[2, 3-b] thiophene, two thieno-[3, 2-b:2 ', 3 '-d] thiophene, carbazole, indoles, 4H-cyclopropyl [2, 1-b:3, 4-b '] two thiophene, 4, 8-bis-alkoxy benzene azoles [1, 2-b:4, 5-b '] two thiophene, 4, the two thieno-[3 of 4 '-bis-alkyl, 2-b:2 ', 3 '-d] thiophene coughs up, benzo [1, 2-b:4, 5-b '] two thiophene.
Alternatively the alkyl of base specifically can be: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, 2-methyl butyl, 3-methyl butyl, 1-ethyl-butyl, 2-ethyl-butyl, 1-butyl, amyl group, isopentyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1-ethyl pentyl group, 2-ethyl pentyl group, 3-ethyl pentyl group, hexyl, isohexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2-ethylhexyl, heptyl, different heptyl, octyl group, iso-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, any one in heptadecyl and octadecyl.
Alternatively the alkoxyl group of base specifically can be: methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, 2-methylbutoxy group, 3-methylbutoxy group, 1-ethyl-butoxy, 2-ethyl-butoxy, 1-propylbutoxy, pentyloxy, isopentyloxy, 2-methyl pentyloxy, 3-methyl pentyloxy, 4-methyl pentyloxy, 1-ethyl pentyloxy, 2-ethyl pentyloxy, 3-ethyl pentyloxy, hexyloxy, different hexyloxy, 2-methyl hexyloxy, 3-methyl hexyloxy, 4-methyl hexyloxy, 5-methyl hexyloxy, 2-ethyl hexyl oxy, heptan oxygen base, different heptan oxygen base, octyloxy, different octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, undecane oxygen base, dodecyloxy, tridecane oxygen base, tetradecyloxyaniline, pentadecane oxygen base, n-Hexadecane oxygen base, any one in heptadecane oxygen base and octadecane oxygen base.
Preferably, the present invention contains the polymkeric substance being with thieno-[3, the 4-b] thiophene conjugated polymer of crosslinked group to can be formula II structure,
(formula II)
Wherein, R is C
1-C
18alkyl; P and q is the natural number of 1-18; A/ (a+b) is the arbitrary value of 0-1 and a/ (a+b) is not 0; N be more than or equal to 4 natural number.
The preparation method of polymkeric substance shown in formula II, comprise the steps: shown in formula III 4,6-dibromo thiophene is 4,6-dibromo thiophenes shown in [3,4-b] thiophene-2-carboxylic acid alkyl ester, formula IV also [3 also, 4-b] thiophene) shown in-2-carboxylic acid bromo alkyl ester and formula V 4,8-bis-(alkoxyl group) benzo [1,2-b:4,5-b '] two thiophene-2,6-bis-(tin trimethyl) reacts under tetra-triphenylphosphine palladium catalysis, obtains the conjugated polymers shown in formula II.
(formula III) (formula IV) (formula V)
The definition cotype II of p in formula III, the definition cotype II of q in formula IV, the definition cotype II of R in formula V.
Here used by 4; 6-dibromo thiophene also [3,4-b] thiophene-2-carboxylic acid alkyl ester is prepared by following steps: by 1-alkyl alcohol and 4,6-dibromo thiophene also [3; 4-b] thiophene-2-carboxylic acid mixing; and adding 1,3-dicyclohexyl diimine and Dimethylamino pyridine, anhydrous methylene chloride makes solvent; nitrogen protection; 4,6-dibromo thiophene also [3,4-b] thiophene-2-carboxylic acid ester is obtained after stirring reaction 5-24 hour.
4,6-dibromo thiophene also [3,4-b] thiophene-2-carboxylic acid bromo alkyl ester is prepared by following steps:
1), after alkyl diol, Hydrogen bromide mix with toluene, at 100-200 DEG C, bromhydrin is obtained after stirring reaction 10-48 hour;
2) by bromhydrin and 4; 6-dibromo thiophene also [3; 4-b] thiophene-2-carboxylic acid mixing; and adding 1,3-dicyclohexyl diimine and Dimethylamino pyridine, anhydrous methylene chloride makes solvent; nitrogen protection; 4,6-dibromo thiophene also [3,4-b] thiophene-2-carboxylic acid bromo alkyl ester is obtained after stirring reaction 5-24 hour.
Two of object of the present invention is to provide this type of thieno-[3,4-b] thiophene conjugated polymer containing band crosslinked group and is preparing the application in photoelectric device, especially in the application preparing polymer solar cells field.
Thieno-[3 containing band crosslinked group of the present invention, 4-b] thiophene conjugated polymer material, be not only a kind of good electron donor material, and can improve the good solubility-resistence of film, the method that employing solution is processed prepares multilayered structure photovoltaic device becomes possibility.
When by Inventive polymers for the preparation of multilayer structure polymer solar cell time, can at the first layer spin coating Inventive polymers, and with ultraviolet or heating or add the modes such as initiator and cause crosslinked, film after crosslinked has stronger good solubility-resistence, then the crosslinkable or not crosslinkable material of the spin coating second layer again on the first layer film, if crosslinkable material, then also can continue spin coating third layer.According to said method just can realize constructing of multilayered structure.
Crosslinkable polymer prepared by the present invention, it can make effectively to freeze to the micro phase separation structure of acceptor in conjugated polymers composite membrane after cross-linking, thus improves the thermostability of device.Crosslinking structure also substantially increases the good solubility-resistence of film simultaneously, and making the method for being processed by solution prepare multilayered structure device becomes possibility.
Accompanying drawing explanation
Fig. 1 be film that in embodiment 1, polymkeric substance is made without UV-crosslinked, be immersed in the UV-vis absorption spectrum figure in orthodichlorobenzene solvent after 5 minutes.
Fig. 2 is that the film that in embodiment 1, polymkeric substance is made is first after UV-crosslinked 5 minutes, then is immersed in the UV-vis absorption spectrum figure in orthodichlorobenzene solvent after 5 minutes.
Fig. 3 is that the film that in embodiment 1, polymkeric substance is made is first after UV-crosslinked 10 minutes, then is immersed in the UV-vis absorption spectrum figure in orthodichlorobenzene solvent after 5 minutes.
Fig. 4 is that the film that in embodiment 1, polymkeric substance is made is first after UV-crosslinked 20 minutes, then is immersed in the UV-vis absorption spectrum figure in orthodichlorobenzene solvent after 5 minutes.
Fig. 5 is the current-voltage curve measured by photovoltaic device (crosslinked 5 minutes of ultraviolet lighting, anneals 90 minutes) that in embodiment 1 prepared by polymkeric substance.
Fig. 6 is the current-voltage curve measured by photovoltaic device (non-ultraviolet lighting is cross-linked, and anneals 90 minutes) that in embodiment 1 prepared by polymkeric substance.
Fig. 7 is the current-voltage curve measured by photovoltaic device (non-ultraviolet lighting is cross-linked, unannealed) that in embodiment 1 prepared by polymkeric substance.
Embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
The conjugated polymers 1 of embodiment 1, preparation formula 1 structure
The conjugated polymers 1 of formula 1 structure is the thieno-[3 of alkyl chain end strips bromine crosslinked group, 4-b] thiophene and the thieno-not with bromine crosslinked group [3,4-b] thiophene and [4,8-bis-(different octyloxy) benzo [1,2-b:4,5-b '] terpolymer of two thiophene, its concrete reaction formula is as follows:
Formula 1
Concrete preparation method is as follows:
Step 1) 1,8-ethohexadiol 0.1mol mixes with Hydrogen bromide 0.18mol, and solvent made by toluene, stirring reaction 36 hours at 110 DEG C, extraction, and underpressure distillation obtains colourless liquid is the bromo-1-octanol of 8-.
Step 2) 8-bromo-1-octanol 12mmol, 4,6-dibromo thiophene also [3; 4-b] thiophene-2-carboxylic acid 3mmol; 1,3-dicyclohexylcarbodiimide 3.6mmol mixes with Dimethylamino pyridine 1.05mmol, and anhydrous methylene chloride makes solvent; nitrogen protection; stirring reaction spends the night, extraction, and purifying with chromatography column obtains 4; 6-dibromo thiophene is [3,4-b] thiophene also)-2-carboxylic acid-8-bromine monooctyl ester.
Step 3) 1-octanol 12mmol, 4,6-dibromo thiophene also [3; 4-b] thiophene-2-carboxylic acid 3mmol; 1,3-dicyclohexylcarbodiimide 3.6mmol mixes with Dimethylamino pyridine 1.05mmol, and anhydrous methylene chloride makes solvent; nitrogen protection; stirring reaction spends the night, extraction, and purifying with chromatography column obtains 4; 6-dibromo thiophene is [3,4-b] thiophene-2-carboxylic acid monooctyl ester also.
Step 4) 4; 6-dibromo thiophene also [3; 4-b] thiophene-2-carboxylic acid-8-bromine monooctyl ester 0.25mmol, 4,6-dibromo thiophene also [3; 4-b] thiophene-2-carboxylic acid monooctyl ester 0.25mmol; 4,8-bis-(different octyloxy) benzo [1,2-b:4; 5-b '] two thiophene-2; 6-bis-(tin trimethyl) 0.5mmol, toluene 10ml, N; dinethylformamide 2ml; tetra-triphenylphosphine palladium 30mg, mixes in flask, nitrogen protection; be warming up to 110 DEG C, react 15.5 hours.Polymers soln is cooled to room temperature, and slowly pour in methyl alcohol (50mL), the solid polymer separated out carrys out wash-out with methyl alcohol, normal hexane successively in apparatus,Soxhlet's.After finally dissolving with trichloromethane, precipitating is in methyl alcohol, and filter, vacuum-drying obtains conjugated polymers 1 in 1 day.
Structural identification collection of illustrative plates:
1H NMR((δ/ppm，400MHz，CDCl
3)：7.50-8.10(br，4H)，6.52-7.16(br，2H)，4.42(br，4H)，4.02(br，8H)，3.47(t，2H)，0.70-2.49(br，88H).
GPC：Mn＝22.7k.
The conjugated polymers 2 of embodiment 2, preparation formula 2 structure
The conjugated polymers 2 of formula 2 structure is the thieno-[3 of alkyl chain end strips bromine crosslinked group, 4-b] thiophene and the thieno-not with bromine crosslinked group [3,4-b] thiophene and [4,8-bis-(different octyloxy) benzo [1,2-b:4,5-b '] terpolymer of two thiophene, its concrete reaction formula is as follows:
(formula 2)
Concrete preparation method is as follows:
Step 1) 1,8-ethohexadiol 0.1mol mixes with Hydrogen bromide 0.18mol, and solvent made by toluene, stirring reaction 36 hours at 110 DEG C, extraction, and underpressure distillation obtains colourless liquid is the bromo-1-octanol of 8-.
Step 2) 8-bromo-1-octanol 12mmol, 4,6-dibromo thiophene also [3; 4-b] thiophene-2-carboxylic acid 3mmol; 1,3-dicyclohexylcarbodiimide 3.6mmol mixes with Dimethylamino pyridine 1.05mmol, and anhydrous methylene chloride makes solvent; nitrogen protection; stirring reaction spends the night, extraction, and purifying with chromatography column obtains 4; 6-dibromo thiophene is [3,4-b] thiophene also)-2-carboxylic acid-8-bromine monooctyl ester.
Step 3) 1-octanol 12mmol, 4,6-dibromo thiophene also [3; 4-b] thiophene-2-carboxylic acid 3mmol; 1,3-dicyclohexylcarbodiimide 3.6mmol mixes with Dimethylamino pyridine 1.05mmol, and anhydrous methylene chloride makes solvent; nitrogen protection; stirring reaction spends the night, extraction, and purifying with chromatography column obtains 4; 6-dibromo thiophene is [3,4-b] thiophene-2-carboxylic acid monooctyl ester also.
Step 4) 4; 6-dibromo thiophene also [3; 4-b] thiophene-2-carboxylic acid-8-bromine monooctyl ester 0.375mmol, 4,6-dibromo thiophene also [3; 4-b] thiophene-2-carboxylic acid monooctyl ester 0.25mmol; 4,8-bis-(different octyloxy) benzo [1,2-b:4; 5-b '] two thiophene-2; 6-bis-(tin trimethyl) 0.5mmol, toluene 10ml, N; dinethylformamide 2ml; tetra-triphenylphosphine palladium 30mg, mixes in flask, nitrogen protection; be warming up to 110 DEG C, react 15.5 hours.Polymers soln is cooled to room temperature, and slowly pour in methyl alcohol (50mL), the solid polymer separated out carrys out wash-out with methyl alcohol, normal hexane successively in apparatus,Soxhlet's.After finally dissolving with trichloromethane, precipitating is in methyl alcohol, and filter, vacuum-drying obtains conjugated polymers 2 in 1 day.
Structural identification collection of illustrative plates:
1H NMR((δ/ppm，400MHz，CDCl3)：7.50-8.10(br，4H)，6.52-7.16(br，2H)，4.42(br，4H)，4.02(br，8H)，3.47(t，1H)，0.70-2.49(br，89H).
GPC：Mn＝25.3k.
The good solubility-resistence experiment of the conjugated polymers 1 of embodiment 3, embodiment 1 preparation
Step 1) prepare the slide glass 4 of 10mm × 10mm, respectively wash twice with liquid detergent water, intermediate water, acetone, ethanol successively, dry.
Step 2) by slide glass UV ozone process 20 minutes, the solution of 50 microlitres poly-(3,4-ethylenedioxythiophene) (PEDOT:PSS) is spin-coated to slide surface.
Step 3) solution of conjugated polymers 1 prepared by the 10mg/ml embodiment 1 of spin coating 20 microlitre on the film of poly-(3,4-ethylenedioxythiophene) (PEDOT:PSS).
Step 4) under the slide glass that four scribbled film is placed in the wavelength of ultraviolet lamp 254nm, and irradiate 0,5,10,20 minute respectively, and survey film absorption.
Step 5) slide glass to be immersed in orthodichlorobenzene solvent 5 minutes, take out, with acetone rinsing 30 seconds, dry, survey film absorption.
By the film absorption visible absorption spectrum recorded described in embodiment 3 as Figure 1-4, can draw by calculating: uncrosslinked polymeric film is after the submergence of orthodichlorobenzene solvent, film maximum absorbance is 13.3% of maximum absorbance before submergence, illustrate polymeric film major part on slide glass dissolve by orthodichlorobenzene solvent.The polymeric film of UV-crosslinked 5 minutes before solvent submergence rear film maximum absorbance is submergence maximum absorbance 70.0%, the polymeric film of UV-crosslinked 10 minutes before solvent submergence rear film maximum absorbance is submergence maximum absorbance 80.0%, the polymeric film of UV-crosslinked 20 minutes before solvent submergence rear film maximum absorbance is submergence maximum absorbance 85.3%, illustrate crosslinked after polymeric film major part on slide glass not by orthodichlorobenzene dissolution with solvents, thus illustrate that the good solubility-resistence of crosslinked polymeric film is better than the good solubility-resistence of uncrosslinked polymeric film.
The thermostability experiment of embodiment 4, solar cell prepared by the conjugated polymers 1 of embodiment 1
By 5mg conjugated polymers 1 (prepared by embodiment 1) and 7.5mg [6,6]-phenyl-C
60-methyl-butyrate (being called for short PCBM) mixing, add 0.5ml orthodichlorobenzene to dissolve, by spin coating mode at warp poly-(3,4-ethylenedioxythiophene) (PEDOT:PSS) modified conductive glass on prepare one deck and be about the thick film of 150nm, the slice, thin piece having got rid of film is divided into A, B, C tri-crowdes.A, irradiates 5 minutes under ultraviolet lamp 254nm wavelength, anneals 90 minutes at latter 110 DEG C; B, not uv irradiating, anneal 90 minutes at 110 DEG C; C, not uv irradiating, unannealed.Then prepare metal electrode on polymer by the mode calcium of vacuum evaporation and aluminium, obtain solar cell.Fig. 5-7 is the current-voltage curve of above-mentioned three batches of devices respectively, can draw, criticize device compared to C from figure, and the short-circuit current that A, B criticize device all have dropped, and the short-circuit current that B criticizes device declines more.As for open circuit voltage, the open circuit voltage that B criticizes device does not change, and the open circuit voltage that A criticizes device increases.
By simulated solar irradiation (AM 1.5,100Mw/cm
2) recording A, the effciency of energy transfer of B, C tri-batches of devices, calculates, and criticizes device efficiency phase compared to C, and A criticizes device efficiency and on average have dropped 14.2%, B and criticize device efficiency and then on average have dropped 34.8%.Can draw from calculation result, the thermostability of the active coating film after crosslinked is better than the thermostability of uncrosslinked active coating film.
Claims (5)
1. structural formula is such as formula the conjugated polymers shown in II:
Wherein, R is C
1-C
18alkyl; P and q is the natural number of 1-18; A/ (a+b) is the arbitrary value of 0-1 and a/ (a+b) is not 0 and 1; N be more than or equal to 4 natural number.
2. prepare the method for the conjugated polymers shown in formula II described in claim 1, comprise the steps: the compound shown in the compound shown in formula III, formula IV and the compound shown in formula V to react under tetrakis triphenylphosphine palladium catalysis, obtain the conjugated polymers shown in formula II;
In formula III, the definition of p is identical with the definition of p in claim 1, and in formula IV, the definition of q is identical with the definition of q in claim 1, and in formula V, the definition of R is identical with the definition of R in claim 1.
3. method according to claim 2, is characterized in that: described reaction is carried out in nitrogen atmosphere; The temperature of reaction of described reaction is 80-120 DEG C, and the reaction times is 12-24 hour.
4. conjugated polymers according to claim 1 is preparing the application in photoelectric functional device.
5. application according to claim 4, is characterized in that: described photoelectric functional device is polymer solar battery.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| Title |
|---|
| "Synthesis and Characterization of Thieno[3,4-b]thiophene-Based Copolymers Bearing 4-Substituted Phenyl Ester Pendants: Facile Fine-Tuning of HOMO Energy Levels";Tomoyuki Yamamoto et al.;《Macromolecules》;20110816;第44卷;6659-6662 * |
| Tomoyuki Yamamoto et al.."Synthesis and Characterization of Thieno[3,4-b]thiophene-Based Copolymers Bearing 4-Substituted Phenyl Ester Pendants: Facile Fine-Tuning of HOMO Energy Levels".《Macromolecules》.2011,第44卷6659-6662. * |
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| CN102532492A (en) | 2012-07-04 |
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