Collision cross sections of mass-selected even-sized vanadium oxide cluster cations and anions (V2O5)m/2+/- were measured by ion mobility mass spectrometry for m = 2?60. In comparison with the cross sections of the structures predicted by quantum chemical calculations, fullerene-like polyhedral structures were found to be one of the dominant isomer candidates for vanadium oxide cluster cations for the cluster size m ≥ 30. The assigned structures correspond to the structural motifs of polygonal prism and polyhedral structures, which were recently reported for VmOn+/- (m = 12?20) by the authors. In contrast to the cations, a structural transition was found around m = 12 for anions from polygonal prisms (m = 2?10) to compact structures (m = 12?60). These compact structures have densities between those of polyhedral structures and bulk-like structures.
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