Molecular and electronic structure of heteropolycomplexes

The relationship between half-wave reduction potential (Esub(1/2)) and energy of intervalent transition band (v) has been studied for isostructural heteropolyanions with the same charge XM11ZO405-, where X-Si,P; M-W, Mo,V; Z - Mo,Co,Mn. The study has been conducted by recording EPR and X-ray electron spectra of the corresponding heteropolyanions. A linear correlation between Esub(1/2) and v has been established. Intervalent transition is caused by excitation of electron from the orbital localized on the reduced atom to the orbitals localized on the atoms of the coordination sphere. It has been assumed that the lesser electron delocalization along the whole structure, the greater intensity of intervalent transition