Organocatalyzed atom transfer radical polymerization (O-ATRP) has emerged as a powerful method for the synthesis of precision polymeric materials, driven by visible light. The development of successful N,N-diaryl dihydrophenazine and N-aryl phenoxazine photocatalysts (PCs) provides access to polymers with dispersities lower than 1.10 and controlled molecular weights in a polymerization with quantitative initiator efficiency. Insights provided by quantum chemical calculations enabled the design of PCs with photophysical properties rivaling those of the common iridium and ruthenium polypyridyl complexes. The roles of specific PC properties have been explored in context of different polymerization conditions, namely solvent polarity and irradiation intensity. These mechanistic insights, from a combination of computational, physical, and synthetic chemistries have enabled next-generation catalyst design for accessing highly active PCs in an economical fashion.

Mechanism-driven catalyst design for organocatalyzed atom transfer radical polymerization

255th National Meeting (2018)

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