Preparation of Preyssler-type Phosphotungstate with One Central Potassium Cation and Potassium Cation Migration into the Preyssler Molecule to form Di-Potassium-Encapsulated Derivative

[Image: see text] A mono-potassium cation-encapsulated Preyssler-type phosphotungstate, [P(5)W(30)O(110)K](14–) (1), was prepared as a potassium salt, K(14)[P(5)W(30)O(110)K] (1a), by heating mono-bismuth- or mono-calcium-encapsulated Preyssler-type phosphotungstates (K(12)[P(5)W(30)O(110)Bi(H(2)O)] or K(13)[P(5)W(30)O(110)Ca(H(2)O)]) in acetate buffer. Characterization of the potassium salt 1a by single-crystal X-ray structure analysis, (31)P and (183)W nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared spectroscopy, high-resolution electrospray ionization mass spectroscopy, and elemental analysis revealed that one potassium cation is encapsulated in the central cavity of the Preyssler-type phosphotungstate molecule with a formal D(5h) symmetry. Density functional theory calculations have confirmed that the potassium cation prefers the central position of the cavity over a side position, in which no water molecules are coordinated to the encapsulated potassium cation. (31)P NMR and cyclic voltammetry analyses revealed the rapid protonation–deprotonation of the oxygens in the cavity compared to that of other Preyssler-type compounds. Heating of 1a in the solid state afforded a di-K(+)-encapsulated compound, K(13)[P(5)W(30)O(110)K(2)] (2a), indicating that a potassium counter-cation is introduced in one of the side cavities, concomitantly displacing the internal potassium ion from the center to a second side cavity, thus providing a new method to encapsulate an additional cation in Preyssler compounds.