Controlling transformations in the assembly of polyoxometalate clusters: {Mo11V7}, {Mo17V8} and {Mo72V30}

Abstract

The reaction of molybdate with vanadium(V) in the presence of sulfite anions is explored showing how, via cation control, stepwise assembly through the {Mo₁₁V₇} cluster yields a {M₂₅} cluster-based compound, [Mo^VI₁₁V^V₅V^IV₂O₅₂(μ₉-SO₃)(Mo^VI₆V^VO₂₂)]¹⁰⁻ (1a), which was first discovered using cryospray mass spectrometry, whereas switching the cation away from ammonium allows the direct formation of the spherical ‘Keplerate’ {Mo₇₂V₃₀} cluster.