Experimental and computational study of a new wheel-shaped {[W 5O 21] 3[(U VIO 2) 2(μ-O 2)] 3} 30- polyoxometalate

Abstract

A new wheel-shaped polyoxometalate {[W 5O 21] 3[(U VIO 2) 2(μ-O 2)] 3} 30- has been synthesized and structurally characterized. The calculated electrostatic potential reveals the protonation of several μ-oxo bridges reducing the polyoxometalate total charge. A protonated structure computed at the density functional level of theory (DFT) is in good agreement with the experimental fit. This species presents a classical polyoxometalate electronic structure with well-defined metal and oxo bands belonging to its U/W and oxo/peroxo constituents, respectively. Furthermore, fragment calculations indicate that the electronic structures of the uranyl-peroxide and polyoxotugstate fragments are little affected by the nanowheel assembly. © 2012 American Chemical Society.