Investigation of the effect of ion-pair formation on the stability of hydrogen-bond-assisted polyoxometalate aggregates

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The hydrogen-bond assisted dimerization behavior of protonated decavanadate anions has been investigated by using small angle X-ray scattering and NMR spectroscopy. In protophobic solvents such as acetone and acetonitrile, the decavanadate anions form hydrogen-bonded dimers, whereas the dimers dissociate into monomers in protophilic solvents such as 1,4-dioxane and dimethyl sulfoxide. The dimerization behavior of the decavanadate was proved to depend on the protophilic/protophobic nature of the solvents. The stability of the dimers in the presence of tetrapentyl-, tetraoctyl- and tetradecyl-ammonium cations as the counter cations was also investigated.