Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba2M(VO4)2(OH), M = V3+, Mn3+, and Fe3+

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• 作者：Liurukara D. Sanjeewa ; Michael A. McGuire ; Vasile O. Garlea ; Longyu Hu ; George Chumanov ; Colin D. McMillen ; Joseph W. Kolis
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：July 20, 2015
• 年：2015
• 卷：54
• 期：14
• 页码：7014-7020
• 全文大小：387K
• ISSN：1520-510X

文摘

A new series of transition metal vanadates, namely, Ba₂M(VO₄)₂(OH) (M = V³⁺, Mn³⁺, and Fe³⁺), was synthesized as large single crystals hydrothermally in 5 M NaOH solution at 580 掳C and 1 kbar. This new series of compounds is structurally reminiscent of the brackebuschite mineral type. The structure of Ba₂V(VO₄)₂(OH) is monoclinic in space group P2₁/m, a = 7.8783(2) 脜, b = 6.1369(1) 脜, c = 9.1836(2) 脜, 尾 = 113.07(3)掳, V = 408.51(2) 脜³. The other structures are similar and consist of one-dimensional trans edge-shared distorted octahedral chains running along the b-axis. The vanadate groups bridge across edges of their tetrahedra. Structural analysis of the Ba₂Mn(VO₄)₂(OH) analogue yielded a new understanding of the Jahn鈥揟eller effect in this structure type. Raman and infrared spectra were investigated to observe the fundamental vanadate and hydroxide vibrational modes. Single-crystal temperature-dependent magnetic studies on Ba₂V(VO₄)₂(OH) reveal a broad feature over a wide temperature range with maximum at 鈭?00 K indicating that an energy gap could exist between the antiferromagnetic singlet ground state and excited triplet states, making it potentially of interest for quantum magnetism studies.