Living Chain-growth Polymerization <italic style="font-style: italic">via</italic> C―S Bond Cleavage

Xin-Yu Liang; Ye-Cheng Zhu; Hai-Gen Xiong; Fu-Jun Guo; Wen-Bin Xie; Qin-Qin Shi; Hui Huang

doi:10.1007/s10118-026-3733-3

Your Location：

Home >

Browse articles >

Living Chain-growth Polymerization via C―S Bond Cleavage

RESEARCH ARTICLE | Updated：2026-09-23

- Living Chain-growth Polymerization via C―S Bond Cleavage
- Living Chain-growth Polymerization via C―S Bond Cleavage
- Chinese Journal of Polymer Science 2026年44卷第10期页码：3308-3313
- Affiliations：
  
  a.College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 101408, China
  b.School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering and Low-Carbon Technology, Tianjin University, Tianjin 300072, China
  c.The International Joint Institute of Tianjin University, Fuzhou 350205, China
- Author bio：
  
  xiewenbin@ucas.ac.cn (W.B.X.)
  shiqinqin@ucas.ac.cn (Q.Q.S.)
  huihuang@tju.edu.cn (H.H.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 52222309, 52173187, 52303019 and 52450063), Beijing Natural Science Foundation (No. Z210017), Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB 0520103), International Partnership Program of the Chinese Academy of Sciences (No. 124GJHZ2023079MI), China Postdoctoral Science Foundation (No. 2024T170904), and Fundamental Research Funds for the Central Universities.;Hui Huang is an editorial board member for Chinese Journal of Polymer Science and was not involved in the editorial review or the decision to publish this article. The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3733-3.Data will be available on request from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-026-3733-3
  中图分类号：
- 收稿：2025-12-26，
  
  录用：2026-04-29，
  
  网络首发：2026-07-02，
  
  纸质出版：2026-10-05
- Accepted：
Scan QR Code
Liang, X. Y.; Zhu, Y. C.; Xiong, H. G.; Guo, F. J.; Xie, W. B.; Shi, Q. Q.; Huang, H. Living chain-growth polymerization via C―S bond cleavage. Chinese J. Polym. Sci. 2026, 44, 3308–3313

Xin-Yu Liang, Ye-Cheng Zhu, Hai-Gen Xiong, et al. Living Chain-growth Polymerization via C―S Bond Cleavage[J]. Chinese Journal of Polymer Science, 2026, 44(10): 3308-3313. DOI: 10.1007/s10118-026-3733-3.
Liang, X. Y.; Zhu, Y. C.; Xiong, H. G.; Guo, F. J.; Xie, W. B.; Shi, Q. Q.; Huang, H. Living chain-growth polymerization via C―S bond cleavage. Chinese J. Polym. Sci. 2026, 44, 3308–3313 DOI： 10.1007/s10118-026-3733-3.

Xin-Yu Liang, Ye-Cheng Zhu, Hai-Gen Xiong, et al. Living Chain-growth Polymerization via C―S Bond Cleavage[J]. Chinese Journal of Polymer Science, 2026, 44(10): 3308-3313. DOI: 10.1007/s10118-026-3733-3. DOI：

摘要

Nickel-catalyzed living chain-growth polymerization

via

C―S bond cleavage was developed using aryl sulfides as monomers. This strategy enabled the controlled synthesis of regioregular poly(3-hexylthiophene) with

up to 12.1 kDa and regioregularity up to 96%.

Abstract

Conjugated polymers are indispensable materials in organic optoelectronics. Living chain-growth polymerization has emerged as a promising strategy for synthesizing conjugated polymers with narrow polydispersity indices. To date

the majority of living chain-growth polymerization protocols have relied on Kumada-type cross-coupling reactions using aryl halides as monomers. Herein

we developed a nickel-catalyzed living chain-growth polymerization method based on carbon–sulfur bond activation

employing aryl sulfides as monomers

which enabled the synthesis of poly(3-hexylthiophene) (P3HT) with a regioregularity exceeding 95%. Kinetic studies confirmed the chain-growth mechanism of the polymerization

while steric hindrance and electronic effects were found to play important roles in regulating the polymerization behavior.

关键词

Keywords

references

Huang, X.; Wang, X.; Zou, Y.; An, M.; Wang, Y. The renaissance of poly(3-hexylthiophene) as a promising hole-transporting material toward efficient and stable perovskite solar cells. Small 2024 , 20 , e2400874..

Xu, X.; Zhang, G.; Yu, L.; Li, R.; Peng, Q. P3HT-based polymer solar cells with 8.25% efficiency enabled by a matched molecular acceptor and smart green-solvent processing technology. Adv. Mater. 2019 , 31 , e1906045..

Geng, Y.; Chen, Y.; Du, M.; Wu, H.; Ma, Z.; Xiao, B.; Wang, H.; Tang, A.; Sun, X.; Zhong, Y.; Zhou, E. Comprehensive insight into the structure contribution of A2-A1-D-A1-A2 acceptor to performance of P3HT solar cells. Adv. Energy Mater. 2024 , 14 , 14..

Jung, E. H.; Jeon, N. J.; Park, E. Y.; Moon, C. S.; Shin, T. J.; Yang, T. Y.; Noh, J. H.; Seo, J. Efficient, stable and scalable perovskite solar cells using poly(3-hexylthiophene). Nature 2019 , 567 , 511..

Xian, K.; Ma, R.; Zhou, K.; Liu, J.; Gao, M.; Zhao, W.; Li, M.; Geng, Y.; Ye, L. Miscibility screening promotes the efficiency and stability of P3HT-based organic solar cells. Aggregate 2023 , 5 , 9..

Mun, S.; Park, Y.; Lee, Y. K.; Sung, M. M. Highly sensitive ammonia gas sensor based on single-crystal poly(3-hexylthiophene) (P3HT) organic field effect transistor. Langmuir 2017 , 33 , 13554..

Yokozawa, T.; Ohta, Y. Transformation of step-growth polymerization into living chain-growth polymerization. Chem. Rev. 2016 , 116 , 1950..

Kiriy, A.; Senkovskyy, V.; Sommer, M. Kumada catalyst-transfer polycondensation: mechanism, opportunities, and challenges. Macromol. Rapid Commun. 2011 , 32 , 1503..

Yokozawa, T.; Suzuki, R.; Nojima, M.; Ohta, Y.; Yokoyama, A. Precision synthesis of poly(3-hexylthiophene) from catalyst-transfer Suzuki−Miyaura coupling polymerization. Macromol. Rapid Commun. 2011 , 32 , 801..

Seo, K. B.; Lee, I. H. ; Lee, J.; Choi, I.; Choi, T. L. A rational design of highly controlled Suzuki–Miyaura catalyst-transfer polycondensation for precision synthesis of polythiophenes and their block copolymers: marriage of palladacycle precatalysts with MIDA-boronates. J. Am. Chem. Soc. 2018 , 140 , 4335..

Lee, J. A.; Luscombe, C. K. Dual-catalytic Ag-Pd system for direct arylation polymerization to synthesize poly(3-hexylthiophene). ACS Macro Lett. 2018 , 7 , 767..

Tkachov, R.; Senkovskyy, V.; Beryozkina, T.; Boyko, K.; Bakulev, V.; Lederer, A.; Sahre, K.; Voit, B.; Kiriy, A. Palladium-catalyzed chain-growth polycondensation of AB-type monomers: high catalyst turnover and polymerization rates. Angew. Chem. Int. Ed. 2014 , 53 , 2402..

Qiu, Y.; Mohin, J.; Tsai, C. H.; Tristram-Nagle, S.; Gil, R. R.; Kowalewski, T.; Noonan, K. J. Stille catalyst-transfer polycondensation using Pd-PEPPSI-IPr for high-molecular-weight regioregular poly(3-hexylthiophene). Macromol. Rapid Commun. 2015 , 36 , 840..

Lohwasser, R. H.; Thelakkat, M. Toward perfect control of end groups and polydispersity in poly(3-hexylthiophene) via catalyst transfer polymerization. Macromolecules 2011 , 44 , 3388..

Senkovskyy, V.; Tkachov, R.; Komber, H.; John, A.; Sommer, J. U.; Kiriy, A. Mechanistic insight into catalyst-transfer polymerization of unusual anion-radical naphthalene diimide monomers: an observation of Ni(0) intermediates. Macromolecules 2012 , 45 , 7770..

Li, Z.; Shi, Q.; Ma, X.; Li, Y.; Wen, K.; Qin, L.; Chen, H.; Huang, W.; Zhang, F.; Lin, Y.; Marks, T. J.; Huang, H. Efficient room temperature catalytic synthesis of alternating conjugated copolymers via C-S bond activation. Nat. Commun. 2022 , 13 , 144..

Wen, X.; Xie, W.; Li, Y.; Ma, X.; Liu, Z.; Han, X.; Wen, K.; Zhang, F.; Lin, Y.; Shi, Q.; Peng, A.; Huang, H. Room temperature anhydrous Suzuki-Miyaura polymerization enabled by C-S bond activation. Angew. Chem. Int. Ed. 2023 , 62 , e202309922..

[Zhang, M.; Zhang, B. B.; Lin, Q.; Jiang, Z.; Zhang, J.; Li, Y.; Pei, S.; Han, X.; Xiong, H.; Liang, X.; Lin, Y.; Wei, Z.; Zhang, F.; Zhang, X.; Wang, Z. X.; Shi, Q.; Huang, H. An efficient direct arylation polycondensation via C-S bond cleavage. Angew. Chem. Int. Ed . 2023 , e202306307..

Xie, W.; Song, Z.; Shi, Q.; Sheng, P.; Xu, G.; Wen, K.; Zhao, L.; Marks, T. J.; Wang, Z. X.; Huang, H. General and selective nickel-electrocatalyzed cross-electrophile C*( sp 2 )-C( sp 2 ) coupling. Proc. Natl. Acad. Sci. U.S.A. 2026 , 123 , e2515413123..

Liang, X.; Mi, C.; Guo, F.; Xie, W.; Shi, Q.; Huang, H. Desulfinative cross-coupling of aryl sodium sulfinate with aryl sulfonium salts. Chin. J. Org. Chem. 2026 , 46 , 1000..

[Ye, S.; Lotocki, V.; Xu, H.; Seferos, D., Group 16 conjugated polymers based on furan, thiophene, selenophene, and tellurophene. Chem. Soc. Rev . 2022 , 51 , 6442..

Liang, X.; Wen, K.; Shi, Q.; Zhang, B. B.; Pei, S.; Lin, Q.; Ma, B.; Wang, S.; Zhang, M.; Li, X.; Wang, Z. X.; Huang, H. The aryl sulfide synthesis via sulfide transfer. Chem. Eur. J. 2022 , 28 , e202200869..

Tamba, S.; Fuji, K.; Nakamura, K.; Mori, A. Nickel(II)-catalyzed cross-coupling polycondensation of thiophenes via C–S bond cleavage. Organometallics 2013 , 33 , 12..

Doubina, N.; Ho, A.; Jen, A. K. Y.; Luscombe, C. K. Effect of initiators on the Kumada catalyst-transfer polycondensation reaction. Macromolecules 2009 , 42 , 7670..

Sui, A.; Shi, X.; Wu, S.; Tian, H.; Geng, Y.; Wang, F. Controlled synthesis of polyfluorenes via Kumada catalyst transfer polycondensation with Ni(acac) 2 /dppp as the catalyst. Macromolecules 2012 , 45 , 5436..

Miyakoshi, R.; Yokoyama, A.; Yokozawa, T. Catalyst-transfer polycondensation. mechanism of Ni-catalyzed chain-growth polymerization leading to well-defined poly(3-hexylthiophene). J. Am. Chem. Soc. 2005 , 127 , 17542..

Wang, Q.; Takita, R.; Kikuzaki, Y.; Ozawa, F. Palladium-catalyzed dehydrohalogenative polycondensation of 2-bromo-3-hexylthiophene: an efficient approach to head-to-tail poly(3-hexylthiophene). J. Am. Chem. Soc. 2010 , 132 , 11420..

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Synergistic Effects of Solvent Vapor Assisted Spin-coating and Thermal Annealing on Enhancing the Carrier Mobility of Poly(3-hexylthiophene) Field-effect Transistors

Structure of Friction-transferred Highly Oriented Poly(3-hexylthiophene) Thin Films

Epoxy-functionalized Cyclohexane-based Ricinoleate Plasticizer: Synthesis, Performance Evaluation, and Plasticizing Mechanism

A Paradigm for BF3 Co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature

Pyrimidoisoindigo-based Polymers for Ambipolar Charge Transport

Living Chain-growth Polymerization via C―S Bond Cleavage

Living Chain-growth Polymerization via C―S Bond Cleavage

DOI：10.1007/s10118-026-3733-3

摘要

Abstract

关键词

Keywords

references