Expanding the Scope of Controlled Radical Polymerization via Cobalt–Tellurium Radical Exchange Reaction

Cobalt-mediated radical polymerization (CMRP) and tellurium-mediated radical polymerization (TERP) were combined for the first time, offering new perspectives in the precision design of macromolecular structures. In particular, the present work highlights the benefits of this strategy for the synthesis of novel poly­(vinyl acetate)-based block copolymers. A range of well-defined poly­(vinyl acetate)­s (PVAc) were first produced via CMRP using the bis­(acetylacetonato)­cobalt­(II) complex (Co­(acac)₂) as a regulating agent. Substitution of a methyltellanyl moiety for Co­(acac)₂ at the ω-chain end of the precursor was then achieved upon treatment with dimethylditelluride. In contrast to the PVAc prepared by TERP, the ones produced by sequential CMRP and Co/Te exchange reaction almost exclusively consist of regular head-to-tail-TeMe chain-end species that can be activated by TERP. Ultimately, a series of monomers problematic in Co­(acac)₂-mediated radical polymerization including <i>N</i>-isopropylacrylamide (NIPAM), 2-(dimethylamino)­ethyl acrylate (ADAME), <i>n</i>-butyl acrylate (BA), isoprene (IP), and vinylimidazole (NVIm) were polymerized by TERP from the PVAc–TeMe macroinitiators leading to novel diblock copolymers that cannot be made by each technique used separately