Discovering efficient catalysts is highly desired in expanding the application of halogen-bonding catalysis. We herein report our findings on applying triaminocyclopropenium (TAC) iodides as highly potent catalysts for halogen-bonding catalyzed...

Discovering efficient catalysts is highly desired in expanding the application of halogen-bonding catalysis. We herein report our findings on applying triaminocyclopropenium (TAC) iodides as highly potent catalysts for halogen-bonding catalyzed living radical polymerization. Promoted by the unique effect of ion-pair strain between the TAC cation and the iodide anion, the TAC iodides showed high catalytic efficiency in the halogen-bonding catalysis toward radical generation, and surpassed the previously reported organic iodide catalysts. With the TAC iodide as catalyst, radical polymerization with a living feature was successfully realized, which shows general applicability with a variety of monomers and produced block copolymers. In addition, the TAC-iodides also showed promising feasibility in catalyzing the radical depolymerization of iodo-terminated polymethacrylates. Noteworthily, the catalytic capacity of the TAC iodides is demonstrated to be closely related to the electronic properties of the TAC cation, which offers a molecular platform for further catalyst screening and optimization.