Unlocking the Photoredox and Photoacid Dual Catalytic Activity of BINOLs for the Development of Organocatalytic Orthogonal Polymerization of ATRP and ROP with Light Regulation

The orthogonality of different types of living polymerizations allows the synthesis of polymers with diverse compositions and functions. However, two or more catalysts are normally required to promote the integrated polymerizations separately, and few could deliver a photocontrol on both polymerizations. Herein, we demonstrate that BINOL (1,1′-bi-2-naphthol) with appropriate modification can be evolved into a type of dual-function photocatalyst that can exhibit both photoredox and photoacid catalytic activity at the same time. This dual photofunction could enable BINOLs to catalyze the metal-free atom transfer radical polymerization and ring-opening polymerization with simultaneous light regulation. The utility of this orthogonal method is further demonstrated in the one-pot synthesis of PMMA-b-PVL block copolymers with good control on both molecular weight and low dispersity.