A series of phospho-polyoxotungstate anions was transferred to the gas phase via electrospray ionization (ESI), and the anions' fragmentation was examined by collision-induced dissociation (CID). The anions included [PW12O40]3-, [P2W18O62]6-, and {Co4(H2O)2][PW9O34]2}10- as well as lacunary and metal-substituted derivatives such as [PW11O39]7- and [MPW11O39]5- (M = Co(II), Ni(II), Cu(II)). Common species observed in the mass spectra arose from protonation and alkali metal cationization of the precursor ions. Additional species arising from the formal loss of oxide from the precursor species were also observed, presumably formed via protonation and the loss of an oxo ligand as water. These processes of protonation/cationization and the loss of water both led to species with reduced gas-phase anionic charges, and their formation appears to be driven by the enhanced effects of Coulombic repulsion in the desolvated species generated during transfer to the gas phase via ESI. Fragmentation of selected species was examined by multistage mass spectrometry experiments employing CID. Fragmentation occurred via multiple reaction channels, leading to pairs of complementary product anions whose total stoichiometry and charge matched those of the precursor anion. For example, [PW12O40]3- fragmented to give pairs of product ions of general formulas [W(x)O(3x+1)]2- and [PW(12-x)O(39-3x)]- (x = 6-9), with the most intense pair being [W6O19]2- and [PW6O21]-. Similar ions were also observed for fragmentation of [P2W18O61]4- (derived from the loss of water from [P2W18O62]6-). The lacunary and M(II)-substituted lacunary systems fragmented via related pathways, with the latter generating additional fragment ions due to the presence of M(II). These results highlight the usefulness of ESI-MS in the characterization of complex polyoxometalate anion clusters.

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