Topochemical Ring-Opening Polymerization of an Oxathianethione
Alvaro Calderón‐Díaz, Liam A. Ordner, Maximilian G. Bernbeck, Matteo Palesati, Mark Weber, Natalie Stingelin, Will R. Gutekunst
Abstract
High Resolution Image Download MS PowerPoint Slide Single crystals of an enantiopure oxathianethione ( OTT ) were found to spontaneously convert to the corresponding polymer ( POTT ) through topochemical ring-opening polymerization (topoROP). The polymerization proceeds quantitatively and stereospecifically to give crystalline POTT with high molecular weights. The resulting POTT crystals were suitable for structure determination through X-ray crystallography to reveal polymers with right-handed helices with an antiparallel arrangement of polymer chains. Control studies support a concerted nucleophilic substitution mechanism that proceeds in the absence of radical intermediates, and the polymerization is suppressed when the monomer is randomly organized in an amorphous glass. Overall, this represents a distinct class of topochemical polymerization that opens new opportunities to prepare highly crystalline sulfur-containing materials.