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Crystal Growth and Structure Analysis of Ce18W10O57: A Complex Oxide Containing Tungsten in an Unusual Trigonal Prismatic Coordination Environment.
Title Crystal Growth and Structure Analysis of Ce18W10O57: A Complex Oxide Containing Tungsten in an Unusual Trigonal Prismatic Coordination Environment.
Authors D. Abeysinghe; M.D. Smith; J. Yeon; T. Tran; R.Paria Sena; J. Hadermann; S. Halasyamani; H.Czur Loye
Journal Inorg Chem
DOI 10.1021/acs.inorgchem.6b02710
Abstract

The noncentrosymmetric tungstate oxide, Ce18W10O57, was synthesized for the first time as high-quality single crystals via the molten chloride flux method and structurally characterized by single-crystal X-ray diffraction. The compound is a structural analogue to the previously reported La18W10O57, which crystallizes in the hexagonal space group P6?2c. The +3 oxidation state of cerium in Ce18W10O57 was achieved via the in situ reduction of Ce(IV) to Ce(III) using Zn metal. The structure consists of both isolated and face-shared WO6 octahedra and, surprisingly, isolated WO6 trigonal prisms. A careful analysis of the packing arrangement in the structure makes it possible to explain the unusual structural architecture of Ce18W10O57, which is described in detail. The temperature-dependent magnetic susceptibility of Ce18W10O57 indicates that the cerium(III) f(1) cations do not order magnetically and exhibit simple paramagnetic behavior. The SHG efficiency of Ln18W10O57 (Ln = La, Ce) was measured as a function of particle size, and both compounds were found to be SHG active with efficiency approximately equal to that of ?-SiO2.