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Antimonato polyoxovanadate (POV) cluster compounds {M(en) 3 } 3 [V 15 Sb 6 O 42 (H 2 O)  x  ]· n H 2 O (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 Sb 2 O, (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 16 O/ 18 O exchange reactions of oxygen atoms in the cluster periphery with surrounding H 2  18 O, 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 {V 15 } spin polytope and the {M(en) 3 } 2+ complexes, with very weak coupling between these groups.

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

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