Terpyridine‐Terminated Homo and Diblock Copolymer LEGO Units by Nitroxide‐Mediated Radical Polymerization

Abstract Summary: Novel block copolymers were synthesized in a controlled fashion by nitroxide‐mediated radical polymerization starting from a terpyridine‐modified alkoxyamine. An important feature for controlling the efficiency of the polymerization is the presence of excess nitroxide, responsible for the initial rate of deactivation, which eventually leads to a decrease of the polydispersity indices of the desired block copolymer. The materials obtained were characterized by means of 1 H NMR, UV‐vis spectroscopy, and GPC. The complexation of the terpyridine ligands resulted in the formation of A‐B‐[Ru]‐C, A‐B‐[Ru]‐B‐A, and A‐B‐[Fe]‐B‐A metallo‐supramolecular block copolymers. Telechelic polymers bearing a terpyridine end‐group at the α ‐position and a nitroxide at the ω ‐position were prepared in a living fashion by nitroxide‐mediated polymerization. magnified image Telechelic polymers bearing a terpyridine end‐group at the α ‐position and a nitroxide at the ω ‐position were prepared in a living fashion by nitroxide‐mediated polymerization.