Charge Transfer and Partial Oxidation in the Conductive Hydrocarbon-Iodine Complex “2Perylene•3I₂”

It has long been thought that the highly conductive complexes formed between elemental iodine and various polycyclic aromatic hydrocarbons are molecular complexes; i.e., they contain iodine as I₂. In this contribution we report resonance Raman and iodine-129 Mössbauer spectroscopic characterization of the form of the iodine in the most highly conductive of these materials : “2Perylene•3I₂”. We find that “2Perylene•3I₂”is not a molecular complex, but rather a partially oxidized, mixed-valence compound, the charge distribution of which can be approximately formulated on the basis of the spectral data as (perylene)^+0.4(I₃-•2I₂)_0.4.