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A dodecavanadate, [V₁₂O₃₂]⁴¯, is an inorganic bowl-type host with a cavity entrance with a diameter of 4.4 Å in the optimized structure. The linear, bent, and trigonal planar anions, are tested as a guest anion and the formation of host-guest complexes, [V₁₂O₃₂(X)]⁵¯ (X = CN¯, OCN¯, NO₂¯, NO₃¯, HCO₂¯, and CH₃CO₂¯) were confirmed by X-ray crystallographic analyses and ⁵¹V NMR study. The degree of the distortion of the bowl from a regular bowl to an oval bowl depends on the shape of the guest anion, after host-guest complex formation. In ⁵¹V NMR spectroscopy, all the chemical shifts of the host-guest complexes are clearly shifted after the guest incorporation. The incorporation reaction rates for OCN¯, NO₂¯, HCO₂¯, and CH₃CO₂¯ are much larger than those of NO₃¯ and halides. The incorporated non-spherical molecular anions in the dodecavanadate host are easily dissociated or exchanged to other anions, while the spherical halides in the dodecavanadate host are preserved without dissociation even in the presence of the tested anions.
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Name: Chemistry, an Asian journal
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