Oxidative Direct Arylation Polymerization Using Oxygen as the Sole Oxidant: Facile, Green Access to Bithiazole‐Based Polymers

The most appealing oxidant, molecular oxygen, is employed for the first time as the sole oxidant in the transition metal-catalyzed oxidative direct arylation polymerization (C−H/C−H-type DArP), which eliminates by-product formation of stoichiometric metal salts except for water . Compared to conventional approaches, other than the avoidance of an end-capping procedure, the current protocol is remarkably advanced in the aspect of eco-friendliness, step- and cost-economy, and, of special significance, the purity of polymer products. As illustrative examples, six 5,5′-bithiazole-based polymers are synthesized using this new method, demonstrating higher number-average molecular weight (Mn up to 33 700) in better yields (up to 93 %) through only one step. The evolution of C−H/C−H-type DArP from heavy metal salts to O2 alone as the oxidant could solve the problem of metal residues in polymers, which is considered harmful to the performance of devices.