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Density functional theory is used to explore the locus and consequences of protonation in [Zn4(HO)2(PW9O34)2]10-. The results are used to explain recent observations regarding the contrasting pH effects on the water-ligand exchange in [Mn4(H2O)2(P2W15O56)2]16- and [Co4(H2O)2(P2W15O56)2]16-, and the general effect of protonation on solvent exchange in metal oxides is discussed.

Protonation and water exchange kinetics in sandwich polyoxometalates