This Review highlights our development of highly efficient and selective palladium catalysts for direct arylation polymerization (DArP). P(2-MeOC6H4)3 (L1) serves as a key supporting ligand that maintains reactive mononuclear Pd species. Coligands (TMEDA or XPhos) suppress side reactions and facilitate the activation of less reactive C–X bonds. Operating in polymer-solubilizing media (e.g., THF or toluene), these systems yield π-conjugated polymers with number-average molecular weights of up to 347,700 and cross-coupling selectivities of up to >99%; the resulting materials exhibit device-grade performance comparable to that of polymers prepared by conventional Stille coupling.
