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Issue 4, 2016
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Catalysis of “outer-phase” oxygen atom exchange reactions by encapsulated “inner-phase” water in {V15Sb6}-type polyoxovanadates

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Abstract

Antimonato polyoxovanadate (POV) cluster compounds {M(en)3}3[V15Sb6O42(H2O)xnH2O (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.

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

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Publication details

The article was received on 27 Nov 2015, accepted on 08 Jan 2016 and first published on 08 Jan 2016


Article type: Edge Article
DOI: 10.1039/C5SC04571A
Citation: Chem. Sci., 2016,7, 2684-2694
  • Open access: Creative Commons BY license
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    Catalysis of “outer-phase” oxygen atom exchange reactions by encapsulated “inner-phase” water in {V15Sb6}-type polyoxovanadates

    M. Wendt, U. Warzok, C. Näther, J. van Leusen, P. Kögerler, C. A. Schalley and W. Bensch, Chem. Sci., 2016, 7, 2684
    DOI: 10.1039/C5SC04571A

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