5 years ago

Small-Molecule Anion Recognition by a Shape-Responsive Bowl-Type Dodecavanadate

Small-Molecule Anion Recognition by a Shape-Responsive Bowl-Type Dodecavanadate
Yuji Kikukawa, Yoshihito Hayashi, Sho Kuwajima
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. Linear, bent, and trigonal planar anions are tested as guest anions 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 a 51V NMR spectroscopy study. The degree of distortion of the bowl from a regular to an oval shape depends on the type of guest anion. In 51V NMR spectroscopy, all chemical shifts of the host–guest complexes are clearly shifted after guest incorporation. The incorporation reaction rates for OCN−, NO2−, HCO2−, and CH3CO2− are much larger than those of NO3− and halides. The incorporated nonspherical molecular anions in the dodecavanadate host are easily dissociated or exchanged for other anions, whereas spherical halides in the host are preserved without dissociation, even in the presence of the tested anions. Cavity configurations: Through flexible distortion of a bowl-type dodecavanadate host, molecular anions with nonspherical shapes are stabilized through unique host–guest interactions, even under 1:1 molar ratio conditions (see figure). The anion reception preference of the host in solution has been investigated by 51V NMR spectroscopy.

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

DOI: 10.1002/asia.201700489

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