Crystal chemistry of hydrothermally grown ternary alkali rare earth fluorides.

The structural variations of several alkali metal rare earth fluoride single crystals are summarized. Two different stoichiometric formulations are considered, namely those of ARE2F7 and ARE3F10 (A = K, Rb, Cs; RE = Y, La-Lu), over a wide range of ionic radii of both the alkali and rare earth (RE) ions. Previously reported and several new single-crystal structures are considered. The new single crystals are grown using hydrothermal methods and the structures are compared with literature reports of structures grown from both melts and hydrothermal fluids. The data reported here are combined with the literature data to gain a greater understanding of structural subtleties surrounding these systems. The work underscores the importance of the size of the cations to the observed structure type and also introduces synthetic technique as a contributor to the same. New insights based on single-crystal structure analysis in the work introduce a new disordered structure type in the case of ARE2F7, and examine the trends and boundaries of the ARE3F10 stoichiometry. Such fundamental structural information is useful in understanding the potential applications of these compounds as optical materials.

Hydrothermal Formation of Calcium Copper Tetrasilicate.

We describe the first hydrothermal synthesis of CaCuSi4 O10 as micron-scale clusters of thin platelets, distinct from morphologies generated under salt-flux or solid-state conditions. The hydrothermal reaction conditions are surprisingly specific: too cold, and instead of CaCuSi4 O10 , a porous calcium copper silicate forms; too hot, and calcium silicate (CaSiO3 ) forms. The precursors also strongly impact the course of the reaction, with the most common side product being sodium copper silicate (Na2 CuSi4 O10 ). Optimized conditions for hydrothermal CaCuSi4 O10 formation from calcium chloride, copper(II) nitrate, sodium silicate, and ammonium hydroxide are 350 °C at 3000 psi for 72 h; at longer reaction times, competitive delamination and exfoliation causes crystal fragmentation. These results illustrate that CaCuSi4 O10 is an even more unique material than previously appreciated.