Investigation of the dithieno[3,2-b:2′,3′-d]pyrrole polymerization using cross-coupling and cationic mechanisms

In this manuscript, several methodologies to obtain a living polymerization of dithieno[3,2-b: 2', 3'-d] pyrrole are investigated. First, the CTCP-mechanism (catalyst transfer condensative polymerization) was explored. Polymerizations attempted with this mechanism did not result in the formation of polymer. Additional experiments showed that the monomer does not readily undergo oxidative addition and as a result, polymerization does not occur. A Lewis acid catalyzed polymerization was then attempted and this resulted in the formation of polymer via a polymerization with some living properties. Addition of a sodium phenoxide salt during polymerization resulted in end capping of the polymer. Block copolymers of polydithieno[3,2-b: 2', 3'-d] pyrrole (PDTP) and poly(3-alkoxythiophene) (P3AOT) could also be made.