Multiple Fluorine-Substituted Phosphate Germanium Fluorides and Their Thermal Stabilities.

Author(s) Huang, X.; Liu, B.; Zhuang, R.C.; Pan, Y.; Mi, J.X.; Huang, Y.X.
Journal Inorg Chem
Date Published 2016 Dec 05

Anhydrous compounds are crucially important for many technological applications, such as achieving high performance in lithium/sodium cells, but are often challenging to synthesize under hydrothermal conditions. Herein we report that a modified solvo-/hydro-fluorothermal method with fluoride-rich and water-deficient condition is highly effective for synthesizing anhydrous compounds by the replacement of hydroxyl groups and water molecules with fluorine. Two anhydrous phosphate germanium fluorides, namely, Na3[GeF4(PO4)] and K4[Ge2F9(PO4)], with chainlike structures involving multiple fluorine substitutions, were synthesized using the modified solvo-/hydro-fluorothermal method. The crystal structure of Na3[GeF4(PO4)] is constructed by the common single chains ∞(1){[GeF4(PO4)](3-)} built from alternating GeO2F4 octahedra and PO4 tetrahedra. For K4[Ge2F9(PO4)], it takes the same single chain in Na3[GeF4(PO4)] as the backbone but has additional flanking GeOF5 octahedra via an O-corner of the PO4 groups, resulting in a dendrite zigzag single chain ∞(1){[Ge2F9(PO4)](4-)}. The multiple fluorine substitutions in these compounds not only force them to adopt the low-dimensional structures because of the "tailor effect" but also improve their thermal stabilities. The thermal behavior of Na3[GeF4(PO4)] was investigated by an in situ powder X-ray diffraction experiment from room temperature to 700 °C. The modified solvo-/hydro-fluorothermal method is also shown to be effective in producing the most germanium-rich compounds in the germanophosphate system.

DOI 10.1021/acs.inorgchem.6b02266
ISSN 1520-510X
Citation Huang X, Liu B, Zhuang R-, Pan Y, Mi J-, Huang Y-. Multiple Fluorine-Substituted Phosphate Germanium Fluorides and Their Thermal Stabilities. Inorg Chem. 2016;55(23):12376-12382.

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