Poly(carbyne)s via reductive C1 polymerization

Abstract

C1 polymerizations enable the synthesis of densely functionalized, persubstituted polymers that are challenging to access using conventional methods. One class of C1 polymers are the poly(carbyne)s, which are unique in that they can adopt branched or linear structures, or combinations thereof. Herein, we report the synthesis of new poly(carbyne)s, including those that feature side chains with carbonyl-containing functional groups. The polymers were obtained by exposing solutions of monomers outfitted with trihalomethyl or trimethyl orthoformate groups to metallic lithium, and reaction performance was improved when electron transfer agents (e.g. naphthalene) were included. The mechanisms of the polymerizations were also deconvoluted and found to depend on the monomer employed.