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An Experimental and Computational Study of a New Wheel-shaped {[W5O21]3[(UVIO2)2(μ-O2)]3}30- Polyoxometalate

Miró, P.; Ling, J.; Qiu, J.; Burns, P. C.; Gagliardi, L.; Cramer, C. J.
Inorg. Chem. 2012, 51, 8784 (doi:10.1021/ic3005536).

A new wheel-shaped polyoxometalate {[W5O21]3[(UVIO2)2(μ-O2)]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 nano-wheel assembly.