CN108727567A - Introduce preparation and the purposes of the bioxindol derivative conjugated polymer of heavy atom selenium - Google Patents

Introduce preparation and the purposes of the bioxindol derivative conjugated polymer of heavy atom selenium Download PDF

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CN108727567A
CN108727567A CN201810415099.XA CN201810415099A CN108727567A CN 108727567 A CN108727567 A CN 108727567A CN 201810415099 A CN201810415099 A CN 201810415099A CN 108727567 A CN108727567 A CN 108727567A
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polymer
compound
conjugated polymer
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bioxindol
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赵冬
张清
王筱湛
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Shanghai Jiaotong University
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Abstract

The invention discloses a kind of preparation of bioxindol derivative conjugated polymer introducing heavy atom selenium and purposes；Shown in the conjugated polymer such as formula (I)：R is C8~C20 alkyl chains, 1000 >=n ﹥ 1.The present invention for the first time introduces heavy atom selenium atom in half bioxindol, has synthesized novel monomer.Influence of the introducing of heavy atom to polymer photovoltaic performance is disclosed, the synthesis step of polymer is simple, and yield is high, shows good ultraviolet spectra and absorbs.The introducing of heavy atom can reduce the molar extinction coefficient of polymer, make absorption spectrum Einstein shift.Two kinds of conjugated polymers prepared by the present invention can be used as the donor material in organic semiconductor layer, be applied in polymer solar battery test.In structure I TO/ZnO/polymer:PC61BM/MoO34.28% and 3.36% electricity conversion has been respectively obtained in the test of the organic thin film solar cell of/Ag.

Description

Introduce preparation and the purposes of the bioxindol derivative conjugated polymer of heavy atom selenium
Technical field
The present invention relates to a kind of preparation of bioxindol derivative conjugated polymer introducing heavy atom selenium and purposes.
Background technology
With the increasingly depleted of non-renewable energy resources, facing mankind serious energy crisis, to the profit of regenerative resource It is even more important with just seeming.Development solar cell, which is especially flexible organic solar batteries just, becomes solution energy problem Effective way.
Bioxindol and its derivative are commonly used for the construction unit of organic solar batteries active layer material, because itself has Some excellent properties are such as：Wider absorption region, larger molar extinction coefficient, larger conjugate planes, preferable solubility.
Heavy atom introduce half bioxindol the property of monomer and conjugated polymer can be generated which influence, and to it is organic too The influence of positive energy battery performance, there is presently no reports.The present invention introduces heavy atom by different location, has obtained two kinds of conjugation Polymer has obtained preliminary conclusion, has filled up the property of double of bioxindol of heavy atom and has influenced the blank of research.
Invention content
The object of the present invention is to provide a kind of preparations for the bioxindol derivative conjugated polymer introducing heavy atom selenium And purposes.Specifically be to provide a kind of monomer (SEI) linked based on half bioxindol and selenophen and thiophene copolymers (PSEI-T) and The synthetic method of the copolymer (PTEI-S) of the monomer (TEI) and selenophen of half bioxindol and thiophene link, two kinds of copolymer conducts Application of the donor material in organic polymer solar cell in organic semiconductor active layer.The synthesis side that the present invention discloses Method is simple, yield is high, and obtained Polymer absorption range is wide, and molar extinction coefficient is high, and thermal stability is good, as organic solar Good donor material presents wide application prospect in battery.
The purpose of the present invention is what is be achieved through the following technical solutions：
In a first aspect, the present invention relates to a kind of bioxindol derivative conjugated polymer, the conjugated polymer is such as formula (I) Shown in polymer P TEI-S or PSEI-T：
R is C8~C20 alkyl chains, 1000 >=n ﹥ 1.
Second aspect, the present invention relates to a kind of preparation method of the bioxindol derivative conjugated polymer, the sides Method includes the following steps：
S1, monomer TEIWith double methyl tin selenophensIn Pd2(dba)3As Catalyst, P (o-tol)3It is generation Stille coupling reactions generation polymer P TEI- under conditions of solvent as ligand, toluene S；
S2, monomer SEIWith double methyl tin thiopheneIn Pd2(dba)3As Catalyst, P (O-tol) 3 are generation Stille coupling reactions generation polymer P SEI- under conditions of solvent as ligand, toluene T。
Preferably, the monomer SEI is by compound 1With compound 2In methanol It is generated as generation Knoevenagel condensation reactions under conditions of catalyst as solvent, pyridine.
Preferably, the volume ratio of pyridine and methanol is 1:10~1:100, the molar ratio of compound 1 and compound 2 is 1:1 ~1:1.5.
Preferably, setting-up point is 80~100 DEG C, and condensation reaction time is 12~48 hours.
Preferably, the monomer TEI is by compound 1With compound 5In first Alcohol is generated as solvent, pyridine as generation Knoevenagel condensation reactions under conditions of catalyst.
Preferably, the volume ratio of pyridine and methanol is 1:10~1:100, the molar ratio of compound 1 and compound 5 is 1:1 ~1:1.5.
Preferably, setting-up point is 80~100 DEG C, and condensation reaction time is 12~48 hours.
Preferably, in step S1, the molar ratio of compound TEI and double methyl tin selenophens (compound 3) is 1:1~1:1.5 Reaction temperature is 60~110 DEG C, 3~24 hours reaction time.
Preferably, in step S2, the molar ratio of compound SEI and double methyl tin thiophene (compound 4) is 1:1~1:1.5 Reaction temperature is 60~110 DEG C, 3~24 hours reaction time.
The third aspect, the present invention relates to a kind of bioxindol derivative conjugated polymers as the donor in active layer Purposes of the material in organic thin film solar cell.
Compared with prior art, the present invention has the advantages that：
1, heavy atom selenium is introduced into half bioxindol structure for the first time in the present invention, and the sky by controlling selenophen and thiophene Between position obtain two kinds of polymer, it was found that influence of the heavy atom selenium to the ultra-violet absorption spectrum and electrochemical properties of polymer. The introducing of heavy atom selenium had into great directive significance to people from now on.By on the oxygen atom and thiophene on half bioxindol acyl group Sulphur atom or selenophen on selenium atom between existing non-covalent interaction increase half bioxindol plane and thiophene or The coplanarity of selenophen plane.
2, the synthetic method that the present invention discloses is simple and efficient, and raw material are cheap, and obtained polymer solubility is good, band gap Narrow, ultra-violet absorption spectrum range is wide, is good polymer solar battery donor material, has a good application prospect.
Description of the drawings
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention, Objects and advantages will become more apparent upon：
Fig. 1 is the synthetic route chart of embodiment 1 polymer P SEI-T and PTEI-S；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of 1 compound SEI of embodiment；
Fig. 3 is the nuclear-magnetism carbon spectrogram of 1 compound SEI of embodiment；
Fig. 4 is the nucleus magnetic hydrogen spectrum figure of 1 compound TEI of embodiment；
Fig. 5 is the nuclear-magnetism carbon spectrogram of 1 compound TEI of embodiment；
Fig. 6 is the uv absorption spectra of monomer SEI and TEI in chloroformic solution；
Fig. 7 is the uv absorption spectra of polymer P SEI-T and PTEI-S in chloroformic solution；
Fig. 8 is the solid film uv absorption spectra of polymer P SEI-T and PTEI-S；
Fig. 9 is the cyclic voltammetry curve of polymer P SEI-T and PTEI-S；
Figure 10 is the J-V curves of polymer P SEI-T and PTEI-S.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention Protection domain.
Embodiment 1 prepares half bioxindol derivatives monomer and the conjugated polymer with thiophene and selenophen
Present embodiments provide a kind of half bioxindol derivatives monomer and the system with thiophene and the conjugated polymer of selenophen Preparation Method.Its structural formula is as shown in table 1, synthetic route such as Fig. 1 of monomer and polymer.
Table 1
The present embodiment further relates to the preparation method of polymer P SET-T and PTEI-S, specifically includes following steps：
(a) synthesis of compound 1
The structural formula of compound 1 isThe structural formula of compound TEI isIts Detailed preparation method is shown in document《Jian Wu,Jingde Chen,Hao Huang,Shengxia Li,Hongwei Wu, Chao Hu,Jianxin Tang,and Qing Zhang；(Z)-(Thienylmethylene)oxindole-Based Polymers for HighPerformance Solar Cells.Macromolecules 2016,49,2145-2152》.
(b) synthetic route of compound 2
The structural formula of compound 2 isIts detailed preparation method is shown in document《Dmitry N.Antonov, Leonid I.Belen'Kii, Salo Gronowitz；On the selectivity in the bromination of selenophene‐2‐carbonyl derivatives in the presence of aluminum trichloride：Journal of Heterocyclic Chemistry 1995,32,53-55》.
(c) structural formula of compound 3 and 4 isIts detailed preparation method is shown in document 《Shaohua Shi,Jianyu Yuan,Guanqun Ding,Michael Ford,Kunyuan Lu,Guozheng Shi, Jianxia Sun,Xufeng Ling,Yong Li,and Wanli Ma；Improved All-Polymer Solar Cell Performance by Using Matched Polymer Acceptor：Adv.Funct.Mater.2016,26,5669– 5678》.《Chen,C.H；Hsieh,C.H；Dubosc,M；Cheng,Y.J；HsuC.S；Synthesis and Characterization of Bridged Bithiophene-Based Conjugated Polymers for Photovoltaic Applications:Acceptor Strength and Ternary Blends.Macromolecules 2010,43,697–708.》。
(d) structural formula of compound SEI isIts basic preparation method includes the following steps：
Compound 1 (0.4g, 0.8mmol), compound 2 (0.2g, 0.8mmol), pyridine (1ml), methanol (10ml) are added Enter in bottle with two necks, nitrogen purge gas 15min, the standby pressure of nitrogen are led into bottle with two necks, 100 DEG C of reflux for 24 hours, are cooled to room temperature, rotation is gone Water, dilute hydrochloric acid is added in solvent, and dichloromethane extracts 3 times, merges organic phase, is washed with saturated sodium-chloride, anhydrous MgSO4It is dry, Filtering, is spin-dried for solvent, petroleum ether：Dichloromethane is 20:3 (volume ratios) are eluent, chromatograph post separation, yellow is obtained after being spin-dried for Oily liquids (0.37g, 65%).The nucleus magnetic hydrogen spectrum and carbon spectrogram of the compound SEI of preparation is shown in Fig. 2 and Fig. 3.
(e) structural formula of compound TEI isIts basic preparation method includes the following steps：
Compound 1 (1.9g, 3.8mmol), compound 5 (0.73g, 3.8mmol), pyridine (1ml), methanol (10ml) are added Enter in bottle with two necks, nitrogen purge gas 15min, the standby pressure of nitrogen are led into bottle with two necks, 100 DEG C of reflux for 24 hours, are cooled to room temperature, rotation is gone Water, dilute hydrochloric acid is added in solvent, and dichloromethane extracts 3 times, merges organic phase, is washed with saturated sodium-chloride, anhydrous MgSO4It is dry, Filtering, is spin-dried for solvent, petroleum ether：Dichloromethane is 20:3 (volume ratios) are eluent, chromatograph post separation, yellow is obtained after being spin-dried for Oily liquids (1.97g, 78%).The nucleus magnetic hydrogen spectrum and carbon spectrogram of the compound SEI of preparation is shown in Fig. 4 and Fig. 5.
(f) synthesis of polymer P SEI-T
By SEI (0.1910g, 0.27mmol) and (0.1099g, the 0.3mmol) catalyst of compound 4 Pd in glove box2 (dba)3(tris(dibenzylideneacetone) dipalladium) (0.0037g, 0.0040mmol), ligand P (o-tol)3(three (adjacent methyl) phenyl Phosphorus) (0.0048g, 0.0160mmol) and solvent dry toluene (10ml), it is added in polymerization pipe, tube sealing is simultaneously to slowly warm up to 65 DEG C, polyase 13 .5h is cooled to room temperature, and appropriate absolute methanol is added and a few drop hydrochloric acid are precipitated, and after stirring 2h, filtering obtains Film-form crude product with metallic luster.Product uses methanol, petroleum ether and chloroform Soxhlet extraction successively, chloroform is spin-dried for, in first It is precipitated in alcohol, filters, obtain the film-form copolymer p SEI-T (0.151g, 87.8%) of metallic luster, number-average molecular weight is 122.2kDa, molecular weight distribution 2.7, n=192.
(g) synthesis of polymer P TEI-S
By TEI (0.1998g, 0.3mmol) and (0.1377g, the 0.3mmol) catalyst of compound 3 Pd in glove box2 (dba)3(0.0055g, 0.0060mmol), ligand P (o-tol)3(0.0073g, 0.0240mmol), and solvent dry toluene (10ml) is added in polymerization pipe, and tube sealing is simultaneously to slowly warm up to 65 DEG C, and polyase 13 .5h is cooled to room temperature, and appropriate absolute methanol is added It is precipitated with a few drop hydrochloric acid, after stirring 2h, filtering obtains the film-form crude product with metallic luster.Product uses first successively Alcohol, petroleum ether and chloroform Soxhlet extraction, are spin-dried for chloroform, precipitate in methyl alcohol, and filtering obtains the film-form copolymer of metallic luster PTEI-S (0.174g, 91.1%yield), number-average molecular weight 181.8kDa, molecular weight distribution 2.5, n=285.
The ratio of two kinds of monomers, reaction time, the dissolving of reaction temperature and monomer when the size of n values depends on feeding intake Degree, then for n values with regard to big, the present embodiment controls two kinds of monomer ratios 1 to polymer molecular weight greatly:1, photovoltaic material polymer molecular weight For general control thousands of between hundreds of thousands, molecular weight can then influence greatly very much the form of film when element manufacturing, and then influence device Performance, thus usually n controls are between 1 to 1000.
In addition, the synthesis of compound 1 is typical alkyl substitution, experiments have shown that the reaction is unrelated with alkyl, monomer The synthesis of TEI and SEI is typical Knoevengel reaction, also unrelated with the length of alkyl chain.Polymer P SEI-T and PTEI- The synthesis of S is Still Ou Lian reaction, by it is many it is demonstrated experimentally that no matter the length of alkyl chain how the reaction can smoothly into Row.Therefore R can use arbitrary C8~C20Alkyl chain.
Embodiment 2, half bioxindol derivatives monomer and the ultra-violet absorption spectrum with thiophene and the conjugated polymer of selenophen And electrochemical properties
The present embodiment is related to the nucleus magnetic hydrogen spectrum carbon spectrum of the monomer SEI occurred in embodiment 1, polymer P SEI-T and PTEI-S Ultra-violet absorption spectrum and electrochemical properties.Fig. 2 and Fig. 3 is respectively the nucleus magnetic hydrogen spectrum and carbon spectrum of monomer SEI.Fig. 4 and Fig. 5 difference It is composed for the nucleus magnetic hydrogen spectrum and carbon of monomer SEI.Fig. 6 be the ultra-violet absorption spectrum of monomer SEI and TEI in chloroformic solution, TEI and The maximum absorption band λ of SEImax absRespectively in 372 and 381nm, SEI has the red shift of 9nm relative to TEI, in 330nm to 440nm models The molar extinction coefficient for enclosing interior TEI is almost 2 times of SEI.Illustrate that sulphur atom is substituted for selenium atom and can make mole disappearing for compound Backscatter extinction logarithmic ratio is substantially reduced.Fig. 7 is the absorption spectrum of polymer P TEI-T, PSEI-T and PTEI-S in chloroformic solution, PTEI-S Maximum absorption band λmax absMolar extinction coefficient is 1.42 × 10 at 618nm5M-1cm-1, the absorption maximum of opposite PSEI-T Peak molar extinction coefficient present in 624nm is 0.90 × 105M-1cm-1, red shift 6nm, and the full thiophene reported before is poly- The maximum absorption band of conjunction object PTEI-T molar extinction coefficient present in 611nm is 1.94 × 105M-1cm-1.Similarly it is polymerizeing Introducing in object due to heavy atom selenium significantly reduces the molar extinction coefficient of polymer.Fig. 8 be polymer P TEI-T, The solid film ultra-violet absorption spectrum of PSEI-T and PTEI-S, the polymer P SEI-T and PTEI-S containing heavy atom selenium relative to There is the red shift of 25nm and 22nm in full thiophen polymer PTEI-T maximum absorption bands.The end of PSEI-T and PTEI-S absorbs λonset,filmRespectively 805 and 800nm, corresponding diminishes optical energy band gap Eg opt(Eg opt=1240/ λOnset, film) it is respectively 1.52 And 1.53eV, all it is the narrower polymer of band gap compared with polymer P TEI-T.It is understood in polymer by Density function theory Selenophen ring and the dihedral angle of half bioxindol plane are 0.1 ° in PSEI-T, thiophene and half bioxindol plane in polymer P TEI-S Dihedral angle is 0.6 °.Prove that obtained polymer has good coplanarity.Selenium atom in polymer P SEI-T on selenophen It is at a distance between the oxygen atom on amide ringLess than the sum of the van der Waals radius between selenium atom and oxygen atomProve there is interaction between selenium atom and oxygen atom.Selenium atom in polymer P TEI-S on selenophen and amide ring On oxygen atom between distance beLess than the sum of the van der Waals radius between sulphur atom and oxygen atomCard There is interaction between bright sulphur atom and oxygen atom.Fig. 9 is the cyclic voltammetry curve of polymer P SEI-T and PTEI-S.Cycle volt The test of peace method carries out on the electrochemical apparatus of CS-150 models, and using three traditional electrode test systems, platinum disk electrode is work Make electrode, silver/nitric acid silver electrode is reference electrode, and platinum electrode is used as to electrode, and electrolyte is tetra-n-butyl ammonium hexafluorophosphate Acetonitrile solution (0.1M), sweep speed 100mV/s, using ferrocene as standard.The oxidation that ferrocene measures under the system Reduction potential is 0.09eV, and because the energy level of ferrocene under vacuum condition is 4.8eV, the energy level of material can be by the public affairs of following energy level Formula is calculated：ELUMO=-(Ered,onset- 0.09+4.8) eV=- (Ered,onset+4.71)eV、EHOMO=-(Eox,onset-0.09 + 4.8) eV=- (Eox,onset+4.71)eV.The initial oxidation current potential of copolymer p SEI-T distinguishes the corresponding HOMO energy levels of 0.52V For -5.23eV, initial reduction current potential is that the corresponding lumo energies of -1.05V are -3.66eV.The initial oxidation current potential of PTEI-S point It is -5.29eV for the corresponding HOMO energy levels of 0.58eV, initial reduction current potential is that the corresponding lumo energies of -1.01V are -3.70eV.
The photovoltaic performance of embodiment 3, polymer P SEI-T and PTEI-S
The present embodiment is related to the copolymer p SEI-T and PTEI-S of embodiment 1 as the donor material in active layer, fowler Alkene PC61Applications of the BM as acceptor material in organic thin film solar cell.The structure of the solar cell used is ITO/ ZnO/polymer:PC61BM/MoO3/Ag.Polymer solar cell device test transformation efficiency data are shown in Table 2, J-V curves and see Figure 10.The transformation efficiency based on the solar cell device that PSEI-T is donor material of preliminary test is up to 3.36%, base In the transformation efficiency of solar cell device that PTEI-S is donor material be up to 4.28%.The introducing of heavy atom improves out Road voltage, reduces diminishes optical energy band gap, and obtained two kinds of polymer has E smaller compared to PTEI-Tloss, respectively 0.66 And 0.68eV, both less than 0.7eV.
Table 2
Polymer Open-circuit voltage (V) Short circuit current (mA/cm2) Fill factor (%) Transfer efficiency (%)
PSEI-T 0.84 6.59 61 3.36
PTEI-S 0.87 8.49 55 4.28
In conclusion the introducing of heavy atom selenium and the difference of introducing position can generate important shadow to Polymer absorption spectrum It rings, and further influences its electricity conversion.Pass through the sulphur atom or selenium on the oxygen atom and thiophene on half bioxindol acyl group Existing non-covalent interaction increases being total to for half bioxindol plane and thiophene or selenophen plane between selenium atom in pheno Flatness.Obtained polymer solubility is good, and band gap is narrow, and ultra-violet absorption spectrum range is wide, is good polymer solar Battery donor material, has a good application prospect.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow Ring the substantive content of the present invention.

Claims (10)

1. a kind of bioxindol derivative conjugated polymer, the conjugated polymer be the polymer P TEI-S as shown in formula (I) or Polymer P SEI-T：
R is C8~C20 alkyl chains, 1000 >=n ﹥ 1.
2. a kind of preparation method of bioxindol derivative conjugated polymer as described in claim 1, which is characterized in that the side Method includes the following steps：
S1, monomer TEIWith double methyl tin selenophensIn Pd2(dba)3As catalysis Agent, P (o-tol)3It is generation Stille coupling reactions generation polymer P TEI-S under conditions of solvent as ligand, toluene；
S2, monomer SEIWith double methyl tin thiopheneIn Pd2(dba)3As catalysis Agent, P (O-tol) 3 are generation Stille coupling reactions generation polymer P SEI-T under conditions of solvent as ligand, toluene.
3. the preparation method of bioxindol derivative conjugated polymer as claimed in claim 2, which is characterized in that the monomer SEI is by compound 1With compound 2In methanol as solvent, pyridine as catalyst Under conditions of occur Knoevenagel condensation reactions generate.
4. the preparation method of bioxindol derivative conjugated polymer as claimed in claim 3, which is characterized in that pyridine and methanol Volume ratio be 1:10~1:100, the molar ratio of compound 1 and compound 2 is 1:1~1:1.5.
5. the preparation method of bioxindol derivative conjugated polymer as claimed in claim 3, which is characterized in that condensation reaction temperature Degree is 80~100 DEG C, and condensation reaction time is 12~48 hours.
6. the preparation method of bioxindol derivative conjugated polymer as claimed in claim 2, which is characterized in that the monomer TEI is by compound 1With compound 5In methanol as solvent, pyridine as catalysis Occur what Knoevenagel condensation reactions generated under conditions of agent.
7. the preparation method of bioxindol derivative conjugated polymer as claimed in claim 6, which is characterized in that pyridine and methanol Volume ratio be 1:10~1:100, the molar ratio of compound 1 and compound 5 is 1:1~1:1.5；Setting-up point be 80~ 100 DEG C, condensation reaction time is 12~48 hours.
8. the preparation method of bioxindol derivative conjugated polymer as claimed in claim 2, which is characterized in that in step S1, The molar ratio of compound TEI and double methyl tin selenophens is 1:1~1:1.5, reaction temperature is 60~110 DEG C, the reaction time 3~24 Hour.
9. the preparation method of bioxindol derivative conjugated polymer as claimed in claim 2, which is characterized in that in step S2, The molar ratio of compound SEI and double methyl tin thiophene is 1:1~1:1.5, reaction temperature is 60~110 DEG C, the reaction time 3~24 Hour.
10. a kind of bioxindol derivative conjugated polymer as described in claim 1 is having as the donor material in active layer Purposes in machine thin-film solar cells.
CN201810415099.XA 2018-05-03 2018-05-03 Introduce preparation and the purposes of the bioxindol derivative conjugated polymer of heavy atom selenium Pending CN108727567A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113881019A (en) * 2021-10-18 2022-01-04 福州大学 2-indolone-based polymer donor material and preparation method thereof
CN115093548A (en) * 2022-06-29 2022-09-23 南京邮电大学 Self-degradable conjugated polymer, nano-particles, preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150105520A1 (en) * 2013-10-15 2015-04-16 The Board of Trustees of the Leland Stanford Junior Uninersity Conjugated polymer-based apparatuses, articles and compounds
CN105367561A (en) * 2015-11-19 2016-03-02 上海交通大学 Preparation and use of indole derivative and conjugated polymer thereof
CN105367756A (en) * 2015-11-19 2016-03-02 上海交通大学 Preparation and use of indole derivative and benzodithiophene bis-tin copolymer
CN105418897A (en) * 2015-12-02 2016-03-23 上海交通大学 Conjugated polymer of indole and thiophene compounds as well as preparation method and application thereof
CN105418896A (en) * 2015-12-02 2016-03-23 上海交通大学 Preparation method of conjugated polymer of indole and thiophene compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150105520A1 (en) * 2013-10-15 2015-04-16 The Board of Trustees of the Leland Stanford Junior Uninersity Conjugated polymer-based apparatuses, articles and compounds
CN105367561A (en) * 2015-11-19 2016-03-02 上海交通大学 Preparation and use of indole derivative and conjugated polymer thereof
CN105367756A (en) * 2015-11-19 2016-03-02 上海交通大学 Preparation and use of indole derivative and benzodithiophene bis-tin copolymer
CN105418897A (en) * 2015-12-02 2016-03-23 上海交通大学 Conjugated polymer of indole and thiophene compounds as well as preparation method and application thereof
CN105418896A (en) * 2015-12-02 2016-03-23 上海交通大学 Preparation method of conjugated polymer of indole and thiophene compounds

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113881019A (en) * 2021-10-18 2022-01-04 福州大学 2-indolone-based polymer donor material and preparation method thereof
CN115093548A (en) * 2022-06-29 2022-09-23 南京邮电大学 Self-degradable conjugated polymer, nano-particles, preparation method and application thereof

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