Solvent Effects on the Intramolecular Charge Transfer Character of ,-Diaryl Dihydrophenazine Catalysts for Organocatalyzed Atom Transfer Radical Polymerization.

The nature of intramolecular charge transfer of ,-diaryl dihydrophenazine photocatalysts (PCs) in different solvents is explored in context of their performance in organocatalyzed atom transfer radical polymerization (O-ATRP). PCs having a computationally predicted lowest energy excited state exhibiting charge transfer (CT) character can operate a highly controlled O-ATRP in a wide range of solvent polarities, from non-polar hexanes to highly polar ,-dimethylacetamide. For PCs having a computationally predicted lowest energy excited state not possessing CT character, their ability to operate a controlled O-ATRP is decreased.