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Updated: May 27, 2025

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Cucurbituril-like Giant PolyOxoThiometalate: Structural Analysis and Solution Studies
Jérôme Marrot1, Clément Falaise1, Maya Abou Fadel1
1Institut Lavoisier de Versailles, UMR 8180 CNRS, UVSQ, Université Paris-Saclay, Versailles 78035, France.
Abstract:
Polycondensation processes of metalate ions in the presence of a dinuclear linker {Mo2E2S2}2+ (E = O, S) and weakly chelating ligands such as acetate or sulfate lead to giant polyoxometalate species, assembled through the connection of pentagonal metal-oxo units. While the most popular structural archetype is undoubtedly the Keplerate-type capsule, topologically reminiscent of the fullerene C60, we report here on the formation conditions of a new giant polyoxothiometalate, whose large cylindrical shape resembles that of organic cucurbituril. The [(SO4)20(H120W80Mo40S40O360)]40- anion has been isolated as single crystals suitable for X-ray diffraction analysis, highlighting the large dimensions of the cucurbituril-like assembly, which reaches 24 Å in length and 14 Å in diameter. The solution behavior of this gigantic polyanion was investigated by Raman, UV-vis spectroscopy, and small-angle X-ray scattering, revealing that its structure is maintained in aqueous solution. These overall results open relevant perspectives in the field of supramolecular chemistry.
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