A series of lanthanide containing mixed-valent vanadium (III/IV) silicates of the type CaxLn1−xVSiO5 (Ln = Ce–Nd, Sm–Lu, Y) was synthesized as high quality single crystals from a molten chloride eutectic flux, BaCl2/NaCl. Utilizing Ca metal as the reducing agent, an in-situ reduction of V5+ to V3+/4+ as well as of Ce4+ to Ce3+ was achieved. The structures of 14 reported isostructural compounds were determined by single crystal X-ray diffraction. They crystallize in the tilasite (CaMgAsO4F) structure type in the monoclinic space group C2/c. The extended structure contains 1D chains of VO6 octahedra that are connected to each other via SiO4 groups and (Ca/Ln)O7 polyhedra. The magnetic susceptibility and the field dependent magnetization data were measured for CaxLn1−xVSiO5 (Ln = Ce–Nd, Sm, Gd–Lu, Y), and support the existence of antiferromagnetic behavior at low temperatures.
Journal of Solid State Chemistry – Elsevier
Published: Apr 1, 2018
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