Conjugated Polymers à la Carte from Time-Controlled Direct (Hetero)Arylation Polymerization.

Direct (hetero)arylation polymerization (DHAP) shows great promise for simple, cheap, and environmentally benign preparation of conjugated polymers, but seems to involve a lack of selectivity when different aromatic C-H bonds are present. We report that some time-controlled DHAP reactions can yield well-defined and processable semiconducting polymers. Following these procedures, various aromatic compounds have been efficiently polymerized, including 2,7-dibromofluorene, 2,7-dibromocarbazole, 1,4-dibromobenzene, bithiophene, dithienyl-benzothiadiazole, and diketopyrrolopyrrole derivatives. All resulting polymers have shown comparable, if not slightly better, properties than their Stille- and Suzuki-synthesized analogs. These findings (re)open the door for the low-cost production of many conjugated polymers for plastic electronics.