TY - JOUR
T1 - Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates
T2 - Ba2M(VO4)2(OH), M = V3+, Mn3+, and Fe3+, with Interesting Jahn-Teller and Spin-Liquid Behavior
AU - Sanjeewa, Liurukara D.
AU - McGuire, Michael A.
AU - Garlea, Vasile O.
AU - Hu, Longyu
AU - Chumanov, George
AU - McMillen, Colin D.
AU - Kolis, Joseph W.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/7/20
Y1 - 2015/7/20
N2 - 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. 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. 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 (Graph Presented).
AB - 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. 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. 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 (Graph Presented).
UR - http://www.scopus.com/inward/record.url?scp=84937718876&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.5b01037
DO - 10.1021/acs.inorgchem.5b01037
M3 - Article
AN - SCOPUS:84937718876
SN - 0020-1669
VL - 54
SP - 7014
EP - 7020
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 14
ER -