Regio- and Stereoselective Polymerization of Diynes with Inorganic Comonomer: A Facile Strategy to Conjugated Poly(p‑arylene dihalodiene)s with Processability and Postfunctionalizability

Development of new methodologies for synthesizing polymers with novel structures and unique properties is a fundamentally important area in polymer science. Herein, a novel synthetic strategy to conjugated poly­(p-arylene dihalodiene)­s (PADs) with high regio- and stereoselectivity was developed. In the presence of PdBr2 and CuBr2, the polymerizations of terminal alkynes proceeded smoothly in air without heating to generate PADs in high yields (up to 95.3%) with high molecular weights (Mw up to 915 900). Low-cost inorganic CuBr2 played dual roles as cocatalyst and comonomer. The PADs possessed good solubility and film-forming ability. Their thin films exhibited high refractive indices (1.7149–1.7245) and would be fabricated into well-resolved fluorescent photopatterns by photolithography. Thanks to the vinyl bromine functionality, the PADs could undergo efficient postmodification to afford polymers with more sophisticated structures and applications.