An Efficient Direct Arylation Polycondensation via C−S Bond Cleavage.

The direct arylation polycondensation (DArP) has become one of the most important methods to construct conjugated polymers (CPs). However, the homocoupling side‐reactions of aryl halides and the low regioseletive reactivities of unfunctionalized aryls hinder the development of DArP. Here, an efficient Pd and Cu co‐catalyzed DArP was developed via inert C−S bond cleavage of 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, two‐dimensional grazing‐incidence wide‐angle X‐ray scattering (2D‐GIWAXS), and the charge transport mobilities revealed that the homocoupling reactions were significantly suppressed with high regioselectivity of unfunctionalized aryls, suggesting this method is an excellent choice for synthesizing high performance CPs. [ABSTRACT FROM AUTHOR]