Abstract

The controlled radical polymerization of a variety of acrylate monomers is reported using an Ir-catalyzed visible light mediated process leading to well-defined homo-, random, and block copolymers. The polymerizations could be efficiently activated and deactivated using light while maintaining a linear increase in molecular weight with conversion and first order kinetics. The robust nature of the fac-[Ir3] catalyst allows carboxylic acids to be directly introduced at the chain ends through functional initiators or along the backbone of random copolymers. In contrast to traditional ATRP procedures, low polydispersity block copolymers, poly-b-, poly-b-, and poly-b-, could be prepared with no monomer sequence requirements. These results illustrate the increasing generality and utility of light mediated Ir-catalyzed polymerization as a platform for polymer synthesis. © 2014 American Chemical Society.