Synthesis of Polyfuran and Thiophene-Furan Alternating Copolymers Using Catalyst-Transfer Polycondensation

There is intense interest in the rational design of semiconducting materials to improve organic electronics. Furan is a particularly attractive monomer for building biorenewable and biodegradable π-conjugated frameworks. In this report, regioregular head-to-tail and head-to-head poly(3-hexylfuran) were synthesized using chain-growth polycondensation. The resultant polyfurans have relatively low molecular weights but also low dispersities. The head-to-head polyfuran adopted a nearly identical coplanar backbone conformation as its head-to-tail analog in the solid state, as determined by UV-visible spectroscopy and atomic force microscopy. Extensive aggregation of the furan homopolymer during polymerization led to the investigation of an alternating furan-thiophene copolymer, confirming that furyl-based monomers can polymerize in a chain-growth manner. All of the synthesized polymers are sensitive when exposed to both oxygen and light.