Precise placement of thioester bonds into sequence-controlled polymers containing ABAC-type units

Yanni Xia, Tong Shao, Yue Sun, Jianuo Wang, Chaoyuan Gu, Chengjian Zhang () and Xinghong Zhang ()
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Yanni Xia: Zhejiang University
Tong Shao: Zhejiang University
Yue Sun: Zhejiang University
Jianuo Wang: Zhejiang University
Chaoyuan Gu: Zhejiang University
Chengjian Zhang: Zhejiang University
Xinghong Zhang: Zhejiang University

Nature Communications, 2025, vol. 16, issue 1, 1-11

Abstract: Abstract The precise placement of thioester bonds into sequence-controlled polymers remains a grand challenge. Here, we demonstrate the versatile synthesis of sequence-controlled polymers from the step polymerization of cyclic thioanhydrides (A), diacrylates (B), and diols/diamines (C). In addition to easily accessible diverse monomers, the method is metal-free/catalyst-free, atom-economical, and wide in monomer scope, yielding 107 polymers with >90% yields and weight-average molecular weights of up to 175.4 kDa. The obtained polymers contain ABAC-type repeating units and precisely distributed in-chain thioester and ester (and amide) groups. The chemoselectivity of the polymerization is revealed by density functional theory calculations. The polymer library exhibits considerably tunable performance: glass-transition temperatures of −36–72 °C, melting temperatures of 43–133 °C, degradability, thermoplastics/elastomers, and thioester-based functions. This study furnishes a facile method to precisely incorporate thioester bonds into sequence-controlled polymers.

Date: 2025
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DOI: 10.1038/s41467-025-57208-8

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