Radical Ions, 46. One‐Electron Oxidation of 1,8‐Chalcogen‐Bridged Naphthalenes

Abstract

Abstract The peri‐bridged naphthalenes C 10 H 6 XY with XY = SS, SSe, STe, SeSe, SeTe, TeTe all exhibit low first vertical ionization potentials at about 7.1 eV and, therefore, can be oxidized using AlCl 3 /H 2 CCl 2 . The radical cations generated (XY = SS to SeTe) are stable at room temperature. The chalcogen bridges dominate the species M⋅ ⊕ regarding spin population as well as charge distribution and, correspondingly, the ESR spectra reflect the effect of increasing spin/orbit interaction S < Se < Te: line widths grow and g values raise linearly from 2.0086 (XY = SS) to 2.0409 (XY = SeTe). The PES ionization energies and the ESR coupling constants of sulfur‐bridged derivatives are satisfactorily reproduced by a molecular state parametrized HMO model.