3 years ago

Configurational Isomerism in Polyoxovanadates

Ulrike Warzok, Paul Kögerler, Lisa Mahnke, Jan van Leusen, Wolfgang Bensch, Kirill Yu. Monakhov, Christoph Schalley, Christian Näther, Aleksandar Kondinski
A water-soluble derivative of the polyoxovanadate {V15E6O42} (E = semimetal) archetype enables the study of cluster shell rearrangements driven by supramolecular interactions. A reaction unique to E = Sb, induced exclusively by ligand metathesis in peripheral [NiII(ethylenediamine)] counterions, results in the nearly quantitative formation of the metastable α1* conformational isomer of the {V14Sb8O42} cluster type. Contrary to all other polyoxovanadate shell architectures, this isomer comprises an inward-oriented vanadyl group and is ca. 50 and 12 kJ mol-1 higher in energy than the previously isolated α and isomers, respectively. We discuss this unexpected reaction in light of supramolecular Sb-O···V and Sb-O···Sb contacts manifested in {V14Sb8O42}2 dimers observed in the solid state. ESI MS experiments confirm the stability of these dimers also in solution and in the gas phase. DFT calculations indicate that other, as of yet elusive isomers might be accessible as well.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201712417

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