Molten Salt Synthesis Of A Mixed-Valent Lanthanide(Iii/Iv) Oxychloride With An Unprecedented Sillen X-2(4) Structure: Ce1.3nd0.7o3cl

A new cerium neodymium oxychloride, Ce1.3Nd0.7O3Cl, has been synthesized by precipitation in a LiCl-CaCl2 molten salt by humid argon sparging. Chemical and structure characterization have been undertaken by powder X-ray diffraction, scanning electron microscopy, high-temperature X-ray diffraction, thermogravimetric analysis, and X-ray photoelectron scattering. This oxychloride crystallizes in space group P4/nmm, a = 3.9848(3) angstrom and c = 12.467(2) angstrom, in a new Sillen-type phase represented by the symbol X-2(4) where "quadruple" fluorite-type layers [M4O6], containing Ce-IV in "inner" sublayers and both Ce-III and Nd-III in "outer" sublayers, alternate with double-halide ion sheets. The structure is also described as a stacking of LnOCl and fluorite-type blocks and constitutes the term n = 2 of a possible series (MO2)(n)(NdOCl)(2).