Photomediated controlled radical polymerization is a versatile method to prepare, under mild conditions, various well-defined polymers with complex architecture, such as block and graft copolymers, sequence-controlled polymers, or hybrid materials via surface initiated polymerization. It also provides opportunity to manipulate the reaction through spatiotemporal control. This review presents a comprehensive account of the fundamentals and applications of various photomediated CRP techniques, including atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT), nitroxide mediated polymerization (NMP) and other procedures. In addition, mechanistic aspects of other photomediated methods are discussed. (C) 2016 Elsevier Ltd. All rights reserved.

KM and XP acknowledge support from NSF (CHE 1400052). TJ and JL are grateful for support from the Flemish Fonds Wetenschappelijk Onderzoek (FWO).