Radical Copolymerization Mediated by Unsaturated Metal Sites in Coordination Nanochannels

Radical copolymerization of methyl methacrylate (MMA) and styrene was performed in [Tb(1,3,5-benzenetrisbenzoate)](n) with coordinatively unsaturated metal sites (UMS) immobilized along the one-dimensional nanochannels. A drastic increase in the proportion of MMA units in the resulting copolymers was obtained compared with that obtained from the corresponding solution polymerization systems. Simultaneous coordination of MMA to the UMS is the key to increasing the MMA proportion during the copolymerization in the nanochannels, which was demonstrated by variable temperature IR measurements and several controlled experiments.