ic3005536_si_003.pdf (2.65 MB)
Experimental and Computational Study of a New Wheel-Shaped {[W5O21]3[(UVIO2)2(μ‑O2)]3}30– Polyoxometalate
journal contribution
posted on 2012-08-20, 00:00 authored by Pere Miró, Jie Ling, Jie Qiu, Peter C. Burns, Laura Gagliardi, Christopher J. CramerA 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 nanowheel assembly.