From lanthanide-mediated, high-precision group transfer polymerization of Michael-type monomers, to intelligent, functional materials

A wide range of catalytic systems is already established for the precise polymerization of functional α,β unsaturated monomers. The rare earth metal-mediated group transfer polymerization (REM-GTP) represents a well-known method which not only enables the fast and controlled conversion of (meth)acrylates, but also of other Michael-type monomers, like the stimuli-responsive 2–vinylpyridine (2VP) and dialkyl vinylphosphonates (DAVP). The next step is to connect and combine the defined macromolecules with smart functions. This feature article is focused on the recent application-oriented advances in the fields of 2VP/DAVP (co)polymers synthesized with REM-GTP catalysts. On the one hand, these copolymers function as dual-responsive drug-delivery vehicles, while exhibiting high biocompatibility during cytotoxicity screenings and in vitro studies. On the other hand, post-polymerization functionalization of PDAVPs allows access to polymer-biomolecule conjugates and polymeric fluorescent markers. Combing these two features, p(DEVP-co-2VP), polymerized with a tailor-made initiator, facilitated the complexation of a rhenium compound, resulting in a photocatalytically-active copolymer.