Mechanistic insights into photo-assisted DMF cleavage mediated by charge transfer reaction

•Metal-free amination of perfluoro aromatic compounds occurs in the presence of light.•Charge transfer from solvent to arene rings occurs in an excited state.•The existence of two minima on the excited states correspond to different nature of charge transfers.•There is a marked reduction in reaction-barrier in going from ground to excited state.•Reductive cleavage of carbon-halogen bond generates halide ions.