17O n.m.r. of paramagnetic heteropoly blues. Discrimination between electron delocalisation pathways and between intermolecular electron transfer rates

Abstract

Well-resolved natural-abundance ¹⁷O n.m.r. spectra of paramagnetic mixed valence heteropoly blue anions, recorded with and without the addition of Mn²⁺ to aid in assignment, reveal differences in spin densities that can be related to intramolecular electron delocalisation, and permit estimates of intermolecular electron exchange rate limits.