On the electronic structure of giant polyoxometalates: Mo 132vs. W 72Mo 60

Abstract

The molecular and electronic structure of the spherical Keplerates [{(Mo VI)Mo VI5O 21} 12(Mo V2O 4) 30] 12- (Mo 132) and [{(W VI)W VI5O 21} 12(Mo V2O 4) 30] 12- (W 72Mo 60) has been determined, for the first time, using first-principles density functional theory (DFT) based methods including solvent effects. Computed geometric parameters are in very good agreement with X-ray data, whereas the electronic structure reveals the archetypal nature of polyoxometalates. © 2012 The Royal Society of Chemistry.