Nuclear and electronic contributions to the photoreactivity of iso- and hetero-polyoxomolybdates

Abstract

Ligand-radical intermediates were detected in flash photolysis of the hexa-and octa-molybdates. The transients exhibited absorption spectra with maxima near 460 nm and lifetimes shorter than 1 ns. The photochemical transformations of these complexes are similar to those of the heptamolybdate and heteropolyoxomolybdates. The effect of the molecular structure on the electronic levels of iso- and hetero-polyoxomolybdates was investigated with an extended-Hückel method in order to rationalize their photochemical behaviour.