Chalcogenide‐Doped Anthracenes as Organophotocatalysts for Metal‐Free Atom Transfer Radical Polymerization

Abstract

AbstractOrganocatalytic atom transfer radical polymerization (O‐ATRP) is emerging as a powerful tool for the synthesis of well‐defined, metal‐free polymers, with additional spatiotemporal control by light. Herein, based on the design logic of heteroatom‐doping of polycyclic arenes for photocatalyst development, a series of chalcogenide atom (e.g., O, S, Se, Te)‐doped anthracenes as potential photocatalysts for O‐ATRP is explored. It is found that these heteroatoms have a significant effect on the photophysical and photoredox properties, leading to different performance in the O‐ATRP of methyl methacrylate (MMA). Upon further optimization, the selenium analogues of N‐aryl phenothiazines are successfully identified as effective photocatalysts for O‐ATRP, which can promote a controlled radical polymerization of MMA.