Organocatalyzed Controlled Copolymerization of Perfluorinated Vinyl Ethers and Unconjugated Monomers Driven by Light

Perfluorinated vinyl ethers (PFVEs) are an important category of monomers for producing fluoropolymers that have found broad applications. In this work, by developing a dibenzo­[a,c]­phenothiazine-based organic photoredox catalyst, we realize photo-controlled radical copolymerization of various PFVEs and unconjugated comonomers (e.g., vinyl esters, vinyl amides, and vinyl ethers) with a high reaction efficiency when exposed to visible-light irradiation, affording a large series of main- and side-chain fluorinated copolymers of low dispersities (D̵ = 1.06–1.24) and good chain-end fidelity at excellent conversions of unconjugated comonomers. Furthermore, this method not only facilitates the “ON/OFF” temporal switch of the chain growth with tunable kinetics for the “ON” states upon altering the wavelengths of light sources but also allows photo-controlled chain extensions with copolymers and homopolymers as additional blocks, presenting a facile and versatile platform to customize complex fluoropolymers for material engineering.