Anion-Radical Polymerization of Sulfur- and Selenium-Substituted N-Type Conjugated Polymers

• DOI: 10.1021/acs.macromol.1c00193
• Publication Date: 2021-03-31T17:41:18Z
• Authors: Paniz Pahlavanlu; So Young An; Jenny R. Panchuk; Adam A. Pollit; Dwight S. Seferos
• Keywords: Cobalt-mediated radical polymerization

While controlled chain-growth polymerizations have been developed for a handful of p-type conjugated polymers, most n-type polymers are still synthesized through step-growth methods that offer little to no control over the polymerization. The anion-radical polymerization thiophene-flanked naphthalene diimides has shown exhibit non-living behavior; however, limited few examples varying degrees control. Strategies improve and expand scope this promising methodology not developed. In study, we investigate series oxygenated thionated, thiophene- selenophene-flanked diimides. We show, optical spectroelectrochemical studies, monomers likely consist complex mixture organic radicals with oxidation states. Surprisingly, subtle changes in monomer structure afforded by sulfur selenium substitution result significant polymer synthesis. Notably, polymerize more rapidly reach higher when compared analogues. thionated form complexes signs catalyst insertion, they do undergo These results provide insights into further development as route well-defined polymers.