Structure and Stability of Pentafluoroaniline and 4-Aminononafluorobiphenyl Radical Anions: Optically Detected Electron Paramagnetic Resonance, Time-Resolved Fluorescence, Time-Resolved Magnetic Field Effect, and Quantum Chemical Study.

Radical anions (RAs) are the key intermediates of the selective hydrodefluorination of polyfluoroarenes. We used the techniques of optically detected electron paramagnetic resonance (OD EPR), time-resolved fluorescence, time-resolved magnetic field effect (TR MFE), and the density functional theory to study the possibility of RAs formation from 4-aminononafluorobiphenyl (1) and pentafluoroaniline (2) and estimate their lifetimes and decay channels. To our knowledge, both RAs have not been detected earlier.