文献类型：期刊文献

英文题名：Single-Crystalline Poly(disulfide)s Enabled by PhotoTriggered Topochemical Ring-Opening Polymerization of 1,2-Dithiolane

作者：Zhu, Zheng-Bin[1,2];Li, Xiaoming[1,2];Liu, Ling[1,2];Xu, Yikai[1,2];Qu, Da-Hui[1,2];Tian, He[1,2];Zhang, Qi[1,2]

机构：[1]East China Univ Sci & Technol, Inst Fine Chem.Key Lab Adv Mat, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Feringa Nobel Prize Scientist, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Joint Int Res Lab Precis Chem & Mol Engn, Sch Chem & Mol Engn,Feringa Nobel Prize Scientist, Inst Fine Chem,Frontiers Sci Ctr Materiobiol & Dyn, Shanghai 200237, Peoples R China

年份：2025

卷号：147

期号：46

起止页码：42743

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20254719546977);WOS:【SCI-EXPANDED(收录号:WOS:001593276500001)】；

基金：This work was supported by National Natural Science Foundation of China (grant nos. 22588101, 22475070, and 22025503), Science and Technology Commission of Shanghai Municipality (24DX1400200), the Fundamental Research Funds for the Central Universities, the Program of Introducing Talents of Discipline to Universities (grant no. B16017), Shanghai Pujiang Scholars Program (grant number 23PJ1402100), and Shanghai Chenguang Scholars Program (grant number 23CGA38). The authors thank Xiujun Liu for the assistance with single-crystal analysis. The authors thank Prof. Weijun Zhao for the technical support of X-ray irradiation. The authors thank the staff at the Ceshihui (https://www.Ceshihui.cn/) for their technical support on GPC analysis. The authors thank Research Center of Analysis and Test of East China University of Science and Technology for the help with the characterization.

语种：英文

外文关键词：Covalent bonds - Crystalline materials - Polysulfides - Single crystals

摘要：Topochemical polymerization offers a versatile approach to producing single-crystalline polymers by in situ polymerization in the preorganized solid state. Despite the existing examples of topochemical polymerization based on the formation of strong covalent bonds (e.g., C-C, C-N, and C-O), the construction of single-crystalline polymers mediated by weak yet dynamic covalent bonds, e.g., disulfide bonds, remains elusive. Here, we report a single-crystalline poly(disulfide) by phototriggered topochemical ring-opening polymerization mediated by disulfide exchange. The key design is to control the spatial distance and geometry of the 1,2-dithiolane ring by elaborating side-chain moieties that determine the supramolecular self-assembling. It is found that zigzag-like preorganization facilitates the quantitative single-crystal-to-single-crystal polymerization triggered by UV/visible light or X-ray. The resulted single-crystalline poly(disulfide)s exhibit superior thermostability and solvent resistance compared to the state-of-the-art amorphous poly(disulfide)s. Upon dissolving the crystals with trifluoroacetic acid, the intrinsic dynamicity of poly(disulfide)s could be reactivated to enable depolymerization and yield origin-quality crystalline monomers for polymer regeneration. We anticipate this work as a starting point, bridging dynamic polymers with topochemical polymerization toward dynamic molecular crystals and smart materials.