Preparation of Supramolecular Miktoarm Star Copolymers with a Zinc Phthalocyanine Core through ATRP and RAFT Polymerization.

Topological polymers have attracted considerable attention owing to their unique chemical and physical properties. This study demonstrates the formation of novel supramolecular miktoarm star copolymers with a zinc phthalocyanine (ZnPc) core using metal-ligand coordination interactions. Various linear polymers with pyridyl end groups, poly(methyl methacrylate), poly(vinyl acetate) and poly(N-vinyl carbazole), are prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. This facilitates coordination to the ZnPc core of 4-armed star-shaped polystyrene prepared via atom-transfer radical polymerization (ATRP). Furthermore, the formation of a 1:1 complex of a ZnPc molecule and pyridyl group of the chain-transfer agent for RAFT is confirmed by absorption spectral studies and 1 H NMR spectroscopic analyses. The concept of supramolecular complexation can be extended to the preparation of AB4 -type supramolecular miktoarm star-shaped copolymers with functional cores.