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Updated: Jun 4, 2026

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes
Published on: November 21, 2017
Stereoselective Ring-Opening Polymerization of Racemic Dithiolactones Assisted by Non-Classical C─H⋯X Interactions
Yanchao Wang1, Chenyang Guo1, Xue Wang1
1State Key Laboratory of Polymer Science and Technology, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, P.R. China.
Abstract:
Stereoselective polymerization offers a powerful route to the synthesis of high-performance recyclable polymers, yet achieving rapid, controlled, and stereoselective chain growth remains challenging. Here, we introduce a catalytic system that is consistent with non-classical C─H⋯X (X = O, S) hydrogen-bonding interactions, in which a bulky quaternary ammonium cation creates a confined environment that orients both the monomer and the propagating chain end through weak yet directional interactions, thereby promoting highly stereoselective ring opening. This system enables ultrafast and stereoselective ring-opening polymerization of chemically recyclable rac-dithiolactones in dichloromethane (DCM), yielding fully recyclable, stereoregular polythioesters (Pm up to 0.97, Mn up to 225.6 kDa) that form stereocomplexes to boost the Tm from 120.1°C to 224.1°C and deliver polyolefin-like mechanical performance. More broadly, these results implicate non-classical hydrogen-bonding interactions in stereocontrol and offer a robust route to stereoregular, chemically recyclable polythioesters.
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