Synthesis, Characterization, and Reactivity of N-Alkyl Phenoxazines in Organocatalyzed Atom Transfer Radical Polymerization.

Core-modified N-alkyl phenoxazines were synthesized and evaluated as photoredox catalysts (PCs) in organocatalyzed atom transfer radical polymerization (O-ATRP). Each PC was characterized and found to strongly absorb UVA and visible light, undergo reversible oxidation to radical cation species, and exhibit high quantum yields of fluorescence (Φf > 77%). PCs found to exhibit intramolecular charge transfer in their excited state were capable of the controlled synthesis of poly(methyl methacrylate) with good molecular weight control (I* ~ 100%) and moderately low dispersity (Đ < 1.30).