An efficient direct arylation polycondensation via C-S bond cleavage

Abstract The direct arylation polycondensation (DArP) has become one of the most important methods to construct conjugated polymers (CPs). However, the homocoupling side-reactions of environmentally-harmful aryl halides and the low regioseletive reactivities of unfunctionalized aryls hinder the development of DArP. Here, we report an efficient Pd and Cu co-catalysis DArP was presented via inert C-S bond cleavage of electron rich aryl thioethers, of which robustness was exemplified by over twenty conjugated polymers (CPs), including copolymers, homopolymers, and random polymers.The capture of oxidative addition intermediate together with experimental and theoretic results suggested the important role of palladium (Pd) and copper (Cu) co-catalysis with a bicyclic mechanism. The studies of NMR, molecular weights, trap densities, X-ray diffraction, and the charge transport mobilities revealed this method is an excellent choice for synthesizing CPs.