VSb(SeO3)4, First Selenite Containing V3+ Cation: Synthesis, Structure, Characterization, Magnetic Properties, and Calculations

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• 作者：Yiseul Shin ; Dong Woo Lee ; Kwang Yong Choi ; Hyun-Joo Koo ; Kang Min Ok
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：December 16, 2013
• 年：2013
• 卷：52
• 期：24
• 页码：14224-14230
• 全文大小：425K
• 年卷期：v.52,no.24(December 16, 2013)
• ISSN：1520-510X

文摘

A new vanadium antimony selenite, VSb(SeO₃)₄, has been synthesized through a solid-state reaction by using V₂O₅, Sb₂O₃, and SeO₂ as reagents. The crystal structure of VSb(SeO₃)₄ has been solved and refined by single-crystal X-ray diffraction. Whereas the starting V⁵⁺ cation has been reduced to V³⁺, the Sb³⁺ cation has been oxidized to Sb⁵⁺ during the synthesis. VSb(SeO₃)₄ has a three-dimensional framework structure consisting of V/SbO₆ octahedra and SeO₃ groups. The V³⁺ and Sb⁵⁺ cations are statistically disordered in the same site with 50% occupancy. The oxide ligands in SeO₃ groups are shared by V/SbO₆ octahedra, and the framework expands outward radially from the center. The effective magnetic moment is estimated to be 渭_eff = 2.57 渭_B per V³⁺ from the magnetic property measurements. The g-factor is determined to be g = 1.9(4) from the electron paramagnetic resonance spectrum, which is typical for a d² ion. The spin-polarized DFT+U calculations with U = 4 and 5 eV exhibit the magnetic moments of 1.98 渭_B and 2.01 渭_B, respectively, on V³⁺ ion. Infrared and UV鈥搗is diffuse reflectance spectra, elemental analysis, X-ray photoelectron spectroscopy, thermal analysis, and electronic structure calculations are also reported.