Aryl Sulfoxide Radical Cations. Generation, Spectral Properties, and Theoretical Calculations

Aromatic sulfoxide radical cations have been generated by pulse radiolysis and laser flash photolysis techniques. In water (pulse radiolysis) the radical cations showed an intense absorption band in the UV region (ca. 300 nm) and a broad less intense band in the visible region (from 500 to 1000 nm) whose position depends on the nature of the ring substituent. At very low pulse energy, the radical cations decayed by first-order kinetics, the decay rate increasing as the pH increases. It is suggested that the decay involves a nucleophilic attack of H2O or OH- (in basic solutions) to the positively charged sulfur atom to give the radical ArSO(OH)CH3•. By sensitized [N-methylquinolinium tetrafluoborate (NMQ+)] laser flash photolysis (LFP) the aromatic sulfoxide radical cations were generated in acetonitrile. In these experiments, however, only the band of the radical cation in the visible region could be observed, the UV band being covered by the UV absorption of NMQ+. The λmax values of the bands in the visible region resulted almost identical to those observed in water for the same radical cations. In the LFP experiments the sulfoxide radical cations decayed by second-order kinetics at a diffusion-controlled rate, and the decay is attributed to the back electron transfer between the radical cation and NMQ•. DFT calculations were also carried out for a number of 4-X ring substituted (X = H, Me, Br, OMe, CN) aromatic sulfoxide radical cations (and their neutral parents). In all radical cations, the conformation with the S−O bond almost coplanar with the aromatic ring is the only one corresponding to the energy minimum. The maximum of energy corresponds to the conformation where the S−O bond is perpendicular to the aromatic ring. The rotational energy barriers are not very high, ranging from 3.9 to 6.9 kcal/mol. In all radical cations, the major fraction of charge and spin density is localized on the SOMe group. However, a substantial delocalization of charge and spin on the ring (almost 50% for the 4-methoxy derivative and around 30% for the other radical cations) is also observed. This suggests some conjugative interaction between the MeSO group and the aromatic system that may become very significant when a strong electron donating substituent like the MeO group is present. The ionization energies (IE) of the 4-X ring substituted neutral aromatic sulfoxides were also calculated, which were found to satisfactorily correlate with the experimental Ep potentials measured by cyclic voltammetry.