Outcompeting Thermodynamics: Ion-Pairing and Coulombic Interactions to Trigger Perfluoroacetate Intra-Ionic Photooxidation for Perfluoroalkylation Reactions

as photosensitizers that oxidize trifluoroacetate without forming ion pairs were ineffective for trifluoromethylation. This probably originates from the more thermodynamically accessible substrate oxidation outcompeting diffusional trifluoroacetate oxidation. The reaction was further exemplified to allow functionalization with a variety of perfluoroalkyl groups of different chain lengths. The approach reported herein could also be used for the removal and/or use of perfluoroalkyl substances (PFAS), often called "forever chemicals", that have recently raised environmental and health concern.