Efficient room temperature catalytic synthesis of alternating conjugated copolymers via C-S bond activation

Zijie Li; Qinqin Shi; Xiaoying Ma; Yawen Li; Kaikai Wen; Linqing Qin; Hao Chen; Wei Huang; Fengjiao Zhang; Yuze Lin; Tobin J Marks; Hui Huang

doi:10.1038/s41467-021-27832-1

Efficient room temperature catalytic synthesis of alternating conjugated copolymers via C-S bond activation

Nat Commun. 2022 Jan 10;13(1):144. doi: 10.1038/s41467-021-27832-1.

Authors

Zijie Li^{1

2}, Qinqin Shi^{3

4}, Xiaoying Ma⁵, Yawen Li⁶, Kaikai Wen¹, Linqing Qin¹, Hao Chen¹, Wei Huang⁷, Fengjiao Zhang⁵, Yuze Lin⁶, Tobin J Marks⁸, Hui Huang^{9

10

11

12}

Affiliations

¹ College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
³ College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China. shiqinqin@ucas.ac.cn.
⁴ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China. shiqinqin@ucas.ac.cn.
⁵ School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
⁶ Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
⁷ Department of Chemistry and the Materials Research Center, Northwestern University, 2145 Sheridan Road, Evanston, IL, 60208, USA.
⁸ Department of Chemistry and the Materials Research Center, Northwestern University, 2145 Sheridan Road, Evanston, IL, 60208, USA. t-marks@northwestern.edu.
⁹ College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China. huihuang@ucas.ac.cn.
¹⁰ Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China. huihuang@ucas.ac.cn.
¹¹ CAS Center for Excellence in Topological Quantum Computation, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China. huihuang@ucas.ac.cn.
¹² CAS Key Laboratory of Vacuum Physic, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China. huihuang@ucas.ac.cn.

Abstract

Structural defects in conjugated copolymers are severely detrimental to the optoelectronic properties and the performance of the resulting electronic devices fabricated from them. Therefore, the much-desired precision synthesis of conjugated copolymers with highly regular repeat units is important, but presents a significant challenge to synthetic materials chemists. To this end, aryl sulfides are naturally abundant substances and offer unrealized potential in cross-coupling reactions. Here we report an efficient room temperature polycondensation protocol which implements aryl disulfide C-S activation to produce defect-minimized semiconducting conjugated copolymers with broad scope and applicability. Thus, a broad series of arylstannanes and thioethers are employed via the present protocol to afford copolymers with number-average molecular weights (M_ns) of 10.0-45.0 kDa. MALDI and NMR analysis of selected copolymers reveals minimal structural defects. Moreover, the polymer trap density here is smaller and the field effect mobility higher than that in the analogous polymer synthesized through thermal-activation Stille coupling.