Band gap and HOMO level control in poly(thienylene vinylene)s prepared by ADMET polymerization

Three dipropenyl monomers were prepared for ruthenium-catalyzed acyclic diene metathesis (ADMET) polymerization. Homopolymerization afforded three poly-(thienylene vinylene)s (PTVs) with distinct optoelectronic properties. Binary combinations of the monomers over a range of compositions gave three series of copolymer samples with tunable HOMO levels and band gaps. The utility of this method was further demonstrated by the preparation of a stoichiometric terpolymer. Polymers were characterized by ¹H NMR spectroscopy, size-exclusion chromatography, ultraviolet-visible spectroscopy, and cyclic voltammetry. This copolymerization approach effectively demonstrates the ability of ADMET polymerization to prepare conjugated copolymers with tuned optoelectronic properties that span a broad composition window.