Atom Transfer Radical Polymerization: A Mechanistic Perspective.

Since its inception, atom transfer radical polymerization (ATRP) has seen continuous evolution in terms of the design of the catalyst and reaction conditions; today, it is one of the most useful techniques to prepare well-defined polymers as well as one of the most notable examples of catalysis in polymer chemistry. This Perspective highlights fundamental advances in the design of ATRP reactions and catalysts, focusing on the crucial role that mechanistic studies play in understanding, rationalizing, and predicting polymerization outcomes. A critical summary of traditional ATRP systems is provided first; we then focus on the most recent developments to improve catalyst selectivity, control polymerizations via external stimuli, and employ new photochemical or dual catalytic systems with an outlook to future research directions and open challenges.