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Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba 2 M(VO 4 ) 2 (OH), M = V 3+ , Mn 3+ , and Fe 3+ , with Interesting Jahn–Teller and Spin-Liquid Behavior

Journal Article · · Inorganic Chemistry
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  1. Clemson Univ., SC (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
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In 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 °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) Å, b = 6.1369(1) Å, c = 9.1836(2) Å, β = 113.07(3)°, V = 408.51(2) Å3. Moreover, 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–Teller effect in this structure type. Raman and infrared spectra were investigated to observe the fundamental vanadate and hydroxide vibrational modes. Finally, single-crystal temperature-dependent magnetic studies on Ba2V(VO4)2(OH) reveal a broad feature over a wide temperature range with maximum at ~100 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.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1265840
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 14 Vol. 54; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (7)

Alkali Transition‐Metal Molybdates: A Stepwise Approach to Geometrically Frustrated Systems journal November 2019
Crystal Structure and Preferential Site Occupancy in Cs6Mn(H2O)2(VO3)8 and Cs5KMn(H2O)2(VO3)8 journal May 2019
Synthesis, characterization, and mechanism analysis of S = 2 quasi-one-dimensional ferromagnetic semiconductor Pb 2 Mn(VO 4 ) 2 (OH) journal January 2016
Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties journal January 2018
Two spin-canted antiferromagnetic orderings and a field-induced metamagnetic transition in SrMn 2 (VO 4 ) 2 (H 2 O) 2 journal January 2019
Single crystal neutron and magnetic measurements of Rb 2 Mn 3 (VO 4 ) 2 CO 3 and K 2 Co 3 (VO 4 ) 2 CO 3 with mixed honeycomb and triangular magnetic lattices journal January 2020
Structural and magnetic characterization of the one-dimensional S = 5 / 2 antiferromagnetic chain system SrMn ( V O 4 ) ( OH ) journal June 2016

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY