The superweak anion B12F122− (Y2−) forms multiple solvation states with alkaline metals (Li+–Cs+) and Ag+ of the form M2Y∙nSolv. These solvated salts have unusual solvation/desolvation properties such as rapid solvation/desolvation at a constant low temperature depending on the solvent vapor above the salt. Herein we report these interesting properties and corresponding crystal structures of these salts of monovalent metal ions of Y2−. The most extensively studied salt, K2Y forms solvated crystals with H2O, HF, CH3CN, CH3NO2, CH3OH, and H2O2 upon crystallization from the appropriate solutions.1 Under the proper conditions K2Y will hydrate and reversibly dehydrate quickly, taking up or losing two equivalents of H2O. Other salts (Li+, Na+, Rb+, and Cs+) of Y2− do not exhibit the rapid hydration/dehydration but do form solvated crystal structures. Differences in solvation states, thermal desolvation and crystal structure will be discussed for K2Y compared to Li2Y, Na2Y, Rb2Y, and Cs2Y. The thermal stability of these salts will also be discussed in relation to their structural properties. Finally, methods to produce highly purified Li2Y and Na2Y for electrolyte materials will be briefly discussed. References 1. Peryshkov, D. V.; Bukovsky, E. V.; Folsom, T. C.; Strauss, S. H., Solid-state solvation and anion packing patterns in X-ray structures of crystalline K2(solv)nB12F12 (solv = H2O2(aq), CH3OH, CH3NO2, and CH3CN). Polyhedron 2013, 58 (0), 197-205.

Solvation/desolvation and crystal structures of monovalent metal salts of the superweak anion B12F122−

249th National Meeting (2015)

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