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Title: 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

Abstract

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.

Authors:
 [1];  [2];  [2];  [1];  [1];  [1];  [1]
  1. Clemson Univ., SC (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1265840
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 14; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sanjeewa, Liurukara D., McGuire, Michael A., Garlea, Vasile O., Hu, Longyu, Chumanov, George, McMillen, Colin D., and Kolis, Joseph W. 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. United States: N. p., 2015. Web. doi:10.1021/acs.inorgchem.5b01037.
Sanjeewa, Liurukara D., McGuire, Michael A., Garlea, Vasile O., Hu, Longyu, Chumanov, George, McMillen, Colin D., & Kolis, Joseph W. 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. United States. doi:10.1021/acs.inorgchem.5b01037.
Sanjeewa, Liurukara D., McGuire, Michael A., Garlea, Vasile O., Hu, Longyu, Chumanov, George, McMillen, Colin D., and Kolis, Joseph W. Wed . "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". United States. doi:10.1021/acs.inorgchem.5b01037. https://www.osti.gov/servlets/purl/1265840.
@article{osti_1265840,
title = {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},
author = {Sanjeewa, Liurukara D. and McGuire, Michael A. and Garlea, Vasile O. and Hu, Longyu and Chumanov, George and McMillen, Colin D. and Kolis, Joseph W.},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.5b01037},
journal = {Inorganic Chemistry},
number = 14,
volume = 54,
place = {United States},
year = {2015},
month = {7}
}

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Works referencing / citing this record:

CSD 1789296: Experimental Crystal Structure Determination: ICSD 251801 : ICSD Structure : H Ba2 O9 V3
dataset, February 2018

  • Sanjeewa, Liurukara D.; McGuire, Michael A.; Garlea, Vasile O.
  • Inorganic Crystal Structure Database
  • DOI: 10.25505/fiz.icsd.cc1y1x74

CSD 1789297: Experimental Crystal Structure Determination: ICSD 251802 : ICSD Structure : H O9 Sr2 V3
dataset, February 2018

  • Sanjeewa, Liurukara D.; McGuire, Michael A.; Garlea, Vasile O.
  • Inorganic Crystal Structure Database
  • DOI: 10.25505/fiz.icsd.cc1y1x85

CSD 1789298: Experimental Crystal Structure Determination: ICSD 251803 : ICSD Structure : H Ba2 Mn O9 V2
dataset, February 2018

  • Sanjeewa, Liurukara D.; McGuire, Michael A.; Garlea, Vasile O.
  • Inorganic Crystal Structure Database
  • DOI: 10.25505/fiz.icsd.cc1y1x96

CSD 1789299: Experimental Crystal Structure Determination: ICSD 251804 : ICSD Structure : H Ba2 Fe O9 V2
dataset, February 2018

  • Sanjeewa, Liurukara D.; McGuire, Michael A.; Garlea, Vasile O.
  • Inorganic Crystal Structure Database
  • DOI: 10.25505/fiz.icsd.cc1y1xb7

Crystal Structure and Preferential Site Occupancy in Cs6Mn(H2O)2(VO3)8 and Cs5KMn(H2O)2(VO3)8
journal, May 2019

  • Pellizzeri, Tiffany M. Smith; McMillen, Colin D.; Ivey, Kimberly
  • Journal of Chemical Crystallography, Vol. 49, Issue 3
  • DOI: 10.1007/s10870-019-00787-4

Synthesis, characterization, and mechanism analysis of S = 2 quasi-one-dimensional ferromagnetic semiconductor Pb 2 Mn(VO 4 ) 2 (OH)
journal, January 2016

  • Zhang, Suyun; Xiang, Hongping; Guo, Wenbin
  • Dalton Transactions, Vol. 45, Issue 16
  • DOI: 10.1039/c6dt00412a

Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties
journal, January 2018

  • Smith Pellizzeri, Tiffany M.; McGuire, Michael A.; McMillen, Colin D.
  • Dalton Transactions, Vol. 47, Issue 8
  • DOI: 10.1039/c7dt04642a

Two spin-canted antiferromagnetic orderings and a field-induced metamagnetic transition in SrMn 2 (VO 4 ) 2 (H 2 O) 2
journal, January 2019

  • Zhang, Su-Yun; Guo, Wen-Bin; He, Zhang-Zhen
  • Dalton Transactions, Vol. 48, Issue 1
  • DOI: 10.1039/c8dt03860k

Alkali Transition‐Metal Molybdates: A Stepwise Approach to Geometrically Frustrated Systems
journal, November 2019

  • Smith Pellizzeri, Tiffany M.; McMillen, Colin D.; Kolis, Joseph W.
  • Chemistry – A European Journal, Vol. 26, Issue 3
  • DOI: 10.1002/chem.201904193

Alkali Transition‐Metal Molybdates: A Stepwise Approach to Geometrically Frustrated Systems
journal, November 2019

  • Smith Pellizzeri, Tiffany M.; McMillen, Colin D.; Kolis, Joseph W.
  • Chemistry – A European Journal, Vol. 26, Issue 3
  • DOI: 10.1002/chem.201904193

Crystal Structure and Preferential Site Occupancy in Cs6Mn(H2O)2(VO3)8 and Cs5KMn(H2O)2(VO3)8
journal, May 2019

  • Pellizzeri, Tiffany M. Smith; McMillen, Colin D.; Ivey, Kimberly
  • Journal of Chemical Crystallography, Vol. 49, Issue 3
  • DOI: 10.1007/s10870-019-00787-4

Synthesis, characterization, and mechanism analysis of S = 2 quasi-one-dimensional ferromagnetic semiconductor Pb 2 Mn(VO 4 ) 2 (OH)
journal, January 2016

  • Zhang, Suyun; Xiang, Hongping; Guo, Wenbin
  • Dalton Transactions, Vol. 45, Issue 16
  • DOI: 10.1039/c6dt00412a

Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties
journal, January 2018

  • Smith Pellizzeri, Tiffany M.; McGuire, Michael A.; McMillen, Colin D.
  • Dalton Transactions, Vol. 47, Issue 8
  • DOI: 10.1039/c7dt04642a

Two spin-canted antiferromagnetic orderings and a field-induced metamagnetic transition in SrMn 2 (VO 4 ) 2 (H 2 O) 2
journal, January 2019

  • Zhang, Su-Yun; Guo, Wen-Bin; He, Zhang-Zhen
  • Dalton Transactions, Vol. 48, Issue 1
  • DOI: 10.1039/c8dt03860k