Wendt, M., Warzok, U., Nather, C., van Leusen, J., Kogerler, P., Schalley, C. A. and Bensch, Wolfgang (2016) Catalysis of "outer-phase" oxygen atom exchange reactions by encapsulated "inner-phase" water in {V15Sb6}-type polyoxovanadates. Chemical Science, 7 (4). pp. 2684-2694. DOI 10.1039/C5SC04571A.

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Abstract

Antimonato polyoxovanadate (POV) cluster compounds {M(en)(3)}(3)[V15Sb6O42(H2O)(x)]center dot nH(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 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 O-16/O-18 exchange reactions of oxygen atoms in the cluster periphery with surrounding (H2O)-O-18, 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.

Document Type:	Article
Additional Information:	Times Cited: 5 Wendt, Michael Warzok, Ulrike Naether, Christian van Leusen, Jan Koegerler, Paul Schalley, Christoph A. Bensch, Wolfgang
Research affiliation:	OceanRep > The Future Ocean - Cluster of Excellence Kiel University
Refereed:	Yes
Open Access Journal?:	No
Publisher:	Nature Research
Projects:	Future Ocean
Date Deposited:	25 Feb 2017 06:53
Last Modified:	17 May 2019 12:36
URI:	https://oceanrep.geomar.de/id/eprint/36371

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