文献类型：期刊文献

英文题名：Library of Stereoregular Polythioesters for Stereocomplex Formation Enabled by Isomerization-Driven Cationic Ring-Opening Polymerization

作者：Yuan, Pengjun[1,2];Xia, Yongliang[2];Zhang, Xi[2];Sun, Yangyang[2];Chen, Yifeng[1];Hong, Miao[2,3]

机构：[1]East China Univ Sci & Technol, Coll Chem & Mol Engn, Key Lab Adv Mat & Joint Int Res Lab Precis Chem &, Shanghai 200237, Peoples R China;[2]Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China;[3]Univ Chinese Acad Sci, Hangzhou Inst Adv Study, Sch Chem & Mat Sci, 1 Sub Lane Xiangshan, Hangzhou 310024, Peoples R China

年份：2025

卷号：64

期号：32

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20252418599541);WOS:【SCI-EXPANDED(收录号:WOS:001505111200001)】；

基金：This work was supported by the National Key R&D Program of China (2021YFA1501700), the National Natural Science Foundation of China (22471286 and 52203020), the Science and Technology Commission of Shanghai Municipality (23XD1424600), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0610000), and the CAS Project for Young Scientists in Basic Research (Grant No. YSBR-094). Dr. Yangyang Sun is thankful for the financial support from Youth Innovation Promotion Association CAS (2022253).

语种：英文

外文关键词：Polythioesters; Ring-opening polymerization; Stereoregular polymer; Supramolecular stereocomplexation; Sustainable polymers

摘要：Supramolecular stereocomplexation is an important tool to advance sustainable polymers, and oxygen-containing polymers represent the most widely studied materials for stereocomplexation. However, the sulfur-containing analogues, a newly emerged class of sustainable polymers, remain essentially unexplored because of a significant challenge encountered in the synthesis of stereoregular polymers and relatively low supramolecular interaction. In this contribution, by the utilization of [Et3O]+[B(C6F5)4]- as a metal-free cationic initiator, controlled isomerization-driven ring-opening polymerizations (IROPs) of nine examples of chiral five-membered thionolactones have been achieved with free or suppressed racemization via unique monomer-stabilized SN2 propagation mechanism, which allows an unprecedented access to a library of new stereoregular polythioesters with high isotacticities (80.0%-99.5%). The investigations into structure-stereocomplexation relationship led to the disclosure of two new polythioester stereocomplexes with high melting temperatures (117.0-161.0 degrees C). The fundamental aspects of stereocomplex formation mechanism and critical factors that affect stereocomplexed ability have also been revealed.