Catalysis of outer-phase oxygen atom exchange reactions by encapsulated inner-phase water in {V15Sb6}-type polyoxovanadates

摘要

Antimonato polyoxovanadate (POV) cluster compounds {M(en)3}3[V15Sb6O42(H2O)x]·nH2O (M = Fe^II, Co^II, Ni^II and x = 0 or 1) obtained under solvothermal conditions exhibit unusual high water solubility making these compounds promising synthons for generation of new POV structure types. Electrospray ionization mass spectrometry provides evidence (i) for a water molecule encapsulated inside the cavity of a fraction of the spherical cluster shells, (ii) for a post-functionalization in water, namely a slow exchange of VO against Sb2O, (iii) for the inner-phase reactivity of the encapsulated water that is capable of opening an oxo-bridge, and (iv) for a significant acceleration of the ¹⁶O/¹⁸O exchange reactions of oxygen atoms in the cluster periphery with surrounding H2¹⁸O, when encapsulated water is present. To the best of our knowledge, this is the first example in polyoxovanadate chemistry for the transduction of inner-phase reactivity of an encapsulated guest molecule into changes in the outer-phase reactivity of the cluster. Magnetic susceptibility measurements reflect the individual contributions of the frustrated {V15} spin polytope and the {M(en)3}²⁺ complexes, with very weak coupling between these groups.