Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties

作者：Pellizzeri Tiffany M Smith; McGuire Michael A; McMillen Colin D; Wen Yimei; Chumanov George; Kolis Joseph W^*

来源：Dalton Transactions, 2018, 47(8): 2619-2627.

DOI：10.1039/c7dt04642a

Two new halide-containing cesium manganese vanadates have been synthesized by a high-temperature (580 degrees C) hydrothermal synthetic method from aqueous brine solutions. One compound, Cs3Mn(VO3)(4)Cl, (1) was prepared using a mixed cesium hydroxide/chloride mineralizer, and crystallizes in the polar non-centrosymmetric space group Cmm2, with a = 16.7820(8) angstrom, b = 8.4765(4) angstrom, c = 5.7867(3) angstrom. This structure is built from sinusoidal zig-zag (VO3)(n) chains that run along the b-axis and are coordinated to Mn2+ containing (MnO4Cl) square-pyramidal units that are linked together to form layers. The cesium cations reside between the layers, but also coordinate to the chloride ion, forming a cesium chloride chain that also propagates along the b-axis. The other compound, Cs2Mn(VO3)(3)F, (2) crystallizes in space group Pbca with a = 7.4286(2) angstrom, b = 15.0175(5) angstrom, c = 19.6957(7) angstrom, and was prepared using a cesium fluoride mineralizer. The structure is comprised of corner sharing octahedral Mn2+ chains, with trans fluoride ligands acting as bridging units, whose ends are capped by (VO3)(n) vanadate chains to form slabs. The cesium atoms reside between the manganese vanadate layers, and also play an integral part in the structure, forming a cesium fluoride chain that runs along the b-axis. Both compounds were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and single-crystal Raman spectroscopy. Additionally, the magnetic properties of 2 were investigated. Above 50 K, it displays behavior typical of a low dimensional system with antiferromagnetic interactions, as to be expected for linear chains of manganese(II) within the crystal structure.

• 出版日期2018-2-28