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 = FeII, CoII, NiII 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.