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Journal of Structural Chemistry

2016 year, number 2

STRUCTURAL FEATURES OF ACIDIC FLUOROPHOSPHATOZIRCONATES (HAFNATES) FROM THE 19F, 31P, 1H NMR DATA

A. B. Slobodyuk1, V. Ya. Kavun1, M. M. Godneva2
1Institute of Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok, Russia
2Institute of Chemistry and Technology of Rare Elements and Mineral Raw Materials, Kola Scientific Center, Russian Academy of Sciences, Apatity, Russia
Keywords: фторофосфатоцирконаты, фторофосфатогафнаты, спектры ЯМР, протонная подвижность, кристаллическое строение, fluorophosphatozirconates, fluorophosphatohafnates, NMR spectra, proton mobility, crystal structure

Abstract

Fluorophosphatometallates with the composition K3H3Zr3F3(PO4)5, Rb3H3Zr3F3(PO4)5, Rb3H3Hf3F3(PO4)5, CsH2Hf2F2(PO4)3×2H2O are studied by 31P, 19F, and 1H NMR. It is found that protons enter in the composition of hydrophosphate groups and fluorine atoms occupy the terminal sites in the tetravalent metal environment. Schemes of the crystal structure of fluorophosphatometallates are proposed. It is established that in CsH2Hf2F2(PO4)3×2H2O water molecules are bonded to the phosphate group proton via a strong hydrogen bond and are characterized by a low energy barrier of molecular motions.