Shotaro Hayashi

3,4‐Appended thiophene monomers furnish unique optoelectronic properties due to electronic and steric effects on the donor unit. Here, we have demonstrated a new polymer synthesis by direct arylation polycondensation of 9,10‐dihydro‐9,10‐[3,4]thiophenoanthracene, a thiophene‐based monomer. Chloride‐promoted direct arylation polycondensation of 9,10‐dihydro‐9,10‐[3,4]thiophenoanthracene with dibromo monomers with acetate in N,N ‐dimethylacetamide gave conjugated alternating copolymers. The obtained polymer had a molecular weight of 38,000 and exhibited high film‐forming ability. The optical and electrochemical properties of the polymers were also discussed.