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Title: Honeycomb-like S = 5/2 Spin–Lattices in Manganese(II) Vanadates

Abstract

We synthesized new complex manganese vanadate materials as high-quality single crystals in multi-millimeter lengths using a high-temperature, high-pressure hydrothermal method. We grew one compound, Mn5(VO4)2(OH)4, from Mn2O3 and V2O5 in 3 M CsOH at 580 °C and 1.5 kbar. Changing the mineralizer to 1 M CsOH/3MCsCl leads to the formation of another product, Mn6O(VO4)2(OH). Both compounds were structurally characterized by single-crystal X-ray diffraction (Mn5(VO4)2(OH)4: C2/m, Z = 2, a = 9.6568(9) Å, b = 9.5627(9) Å, c = 5.4139(6) Å, β = 98.529(8)°; Mn6O(VO4)2(OH): P21/m, Z = 2, a = 8.9363(12) Å, b = 6.4678(8) Å, c = 10.4478(13) Å, β = 99.798(3)°), revealing interesting low-dimensional transition-metal features. Mn5(VO4)2(OH)4 possesses complex honeycomb-type Mn–O layers, built from edge-sharing [MnO6] octahedra in the bc plane, with bridging vanadate groups connecting these layers along the a-axis. Mn6O(VO4)2(OH) presents a more complicated structure with both octahedral [MnO6] and trigonal bipyramidal [MnO5] units. A different pattern of planar honeycomb sheets are formed by edge-shared [MnO6] octahedra, and these sublattices are connected through edge-shared dimers of [MnO5] trigonal bipyramids to form corrugated sheets. Vanadate groups again condense the sheets into a three-dimensional framework. Infrared and Raman spectroscopies indicated the presence of OH groups and displayed characteristicmore » Raman scattering due to vanadate groups. Furthermore, temperature-dependent magnetic studies indicated Curie–Weiss behavior above 100 K with significant anti-ferromagnetic coupling for both compounds, with further complex magnetic behavior at lower temperatures. The data indicate canted anti-ferromagnetic order below 57 K in Mn5(VO4)2(OH)4 and below 45 K in Mn6O(VO4)2(OH). Members of another class of compounds, K2M3(VO4)2(OH)2 (M = Mn, Co), also containing a honeycomb-type sublattice, were also synthesized to allow a comparison of the structural features across all three structure types and to demonstrate extension to other transition metals.« less

Authors:
 [1];  [2];  [1];  [1];  [1];  [1]
  1. Clemson Univ., SC (United States). Dept. of Chemistry and Center for Optical Materials Science and Engineering Technologies
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1352765
Grant/Contract Number:  
AC05-00OR22725; DMR-1410727
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 55; Journal Issue: 18; 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., McMillen, Colin D., Willett, Daniel, Chumanov, George, and Kolis, Joseph W.. Honeycomb-like S = 5/2 Spin–Lattices in Manganese(II) Vanadates. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.inorgchem.6b01286.
Sanjeewa, Liurukara. D., McGuire, Michael A., McMillen, Colin D., Willett, Daniel, Chumanov, George, & Kolis, Joseph W.. Honeycomb-like S = 5/2 Spin–Lattices in Manganese(II) Vanadates. United States. https://doi.org/10.1021/acs.inorgchem.6b01286
Sanjeewa, Liurukara. D., McGuire, Michael A., McMillen, Colin D., Willett, Daniel, Chumanov, George, and Kolis, Joseph W.. Fri . "Honeycomb-like S = 5/2 Spin–Lattices in Manganese(II) Vanadates". United States. https://doi.org/10.1021/acs.inorgchem.6b01286. https://www.osti.gov/servlets/purl/1352765.
@article{osti_1352765,
title = {Honeycomb-like S = 5/2 Spin–Lattices in Manganese(II) Vanadates},
author = {Sanjeewa, Liurukara. D. and McGuire, Michael A. and McMillen, Colin D. and Willett, Daniel and Chumanov, George and Kolis, Joseph W.},
abstractNote = {We synthesized new complex manganese vanadate materials as high-quality single crystals in multi-millimeter lengths using a high-temperature, high-pressure hydrothermal method. We grew one compound, Mn5(VO4)2(OH)4, from Mn2O3 and V2O5 in 3 M CsOH at 580 °C and 1.5 kbar. Changing the mineralizer to 1 M CsOH/3MCsCl leads to the formation of another product, Mn6O(VO4)2(OH). Both compounds were structurally characterized by single-crystal X-ray diffraction (Mn5(VO4)2(OH)4: C2/m, Z = 2, a = 9.6568(9) Å, b = 9.5627(9) Å, c = 5.4139(6) Å, β = 98.529(8)°; Mn6O(VO4)2(OH): P21/m, Z = 2, a = 8.9363(12) Å, b = 6.4678(8) Å, c = 10.4478(13) Å, β = 99.798(3)°), revealing interesting low-dimensional transition-metal features. Mn5(VO4)2(OH)4 possesses complex honeycomb-type Mn–O layers, built from edge-sharing [MnO6] octahedra in the bc plane, with bridging vanadate groups connecting these layers along the a-axis. Mn6O(VO4)2(OH) presents a more complicated structure with both octahedral [MnO6] and trigonal bipyramidal [MnO5] units. A different pattern of planar honeycomb sheets are formed by edge-shared [MnO6] octahedra, and these sublattices are connected through edge-shared dimers of [MnO5] trigonal bipyramids to form corrugated sheets. Vanadate groups again condense the sheets into a three-dimensional framework. Infrared and Raman spectroscopies indicated the presence of OH groups and displayed characteristic Raman scattering due to vanadate groups. Furthermore, temperature-dependent magnetic studies indicated Curie–Weiss behavior above 100 K with significant anti-ferromagnetic coupling for both compounds, with further complex magnetic behavior at lower temperatures. The data indicate canted anti-ferromagnetic order below 57 K in Mn5(VO4)2(OH)4 and below 45 K in Mn6O(VO4)2(OH). Members of another class of compounds, K2M3(VO4)2(OH)2 (M = Mn, Co), also containing a honeycomb-type sublattice, were also synthesized to allow a comparison of the structural features across all three structure types and to demonstrate extension to other transition metals.},
doi = {10.1021/acs.inorgchem.6b01286},
journal = {Inorganic Chemistry},
number = 18,
volume = 55,
place = {United States},
year = {2016},
month = {8}
}

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Works referenced in this record:

A Crystal-Chemical Approach to the Composition and Occurrence of Vanadium Minerals
journal, December 2000


BaMn 9 [VO 4 ] 6 (OH) 2 : A Unique Canted Antiferromagnet with a Chiral “Paddle-Wheel” Structural Feature
journal, November 2014

  • Sun, Kewen; Litvinchuk, Alexander P.; Tapp, Joshua
  • Inorganic Chemistry, Vol. 54, Issue 3
  • DOI: 10.1021/ic502266k

Synthesis and characterization of a pipe-structure manganese vanadium oxide by hydrothermal reaction
journal, January 1999

  • Zhang, Fan; Zavalij, Peter Y.; Stanley Whittingham, M.
  • Journal of Materials Chemistry, Vol. 9, Issue 12
  • DOI: 10.1039/a907465a

Synthesis of polyoxovanadates via “chimie douce”
journal, December 1998


Hydrothermal Synthesis of Vanadium Oxides
journal, October 1998

  • Chirayil, Thomas; Zavalij, Peter Y.; Whittingham, M. Stanley
  • Chemistry of Materials, Vol. 10, Issue 10
  • DOI: 10.1021/cm980242m

AAg 2 (M′ 1/3 M 2/3 )[VO 4 ] 2 : Synthesis, Magnetic Properties, and Lattice Dynamics of Honeycomb-Type Lattices
journal, May 2014

  • Bratsch, Michaela; Tapp, Joshua; Litvinchuk, Alexander P.
  • Inorganic Chemistry, Vol. 53, Issue 10
  • DOI: 10.1021/ic500028b

Synthesis and magnetic properties of a new series of triangular-lattice magnets, Na 2 BaMV 2 O 8 (M = Ni, Co, and Mn)
journal, February 2013


Magnetic structures of the low temperature phase of Mn 3 (VO 4 ) 2 – towards understanding magnetic ordering between adjacent Kagomé layers
journal, January 2016

  • Clemens, Oliver; Rohrer, Jochen; Nénert, Gwilherm
  • Dalton Transactions, Vol. 45, Issue 1
  • DOI: 10.1039/C5DT03141A

Crystal growth, structure, and properties of manganese orthovanadate Mn3(VO4)2
journal, January 2000


A Ag 2 M [VO 4 ] 2 ( A = Ba , Sr ; M = Co , Ni ): A series of ferromagnetic insulators
journal, June 2012


Experimental Realization of a Unique Class of Compounds: XY -Antiferromagnetic Triangular Lattices, KAg 2 Fe[VO 4 ] 2 and RbAg 2 Fe[VO 4 ] 2 , with Ferroelectric Ground States
journal, October 2014

  • Amuneke, Ngozi E.; Tapp, Joshua; de la Cruz, Clarina R.
  • Chemistry of Materials, Vol. 26, Issue 20
  • DOI: 10.1021/cm5025712

Frustrated magnetism in the S = 1 kagomé lattice BaNi3(OH)2(VO4)2
journal, January 2012

  • Freedman, Danna E.; Chisnell, Robin; McQueen, Tyrel M.
  • Chem. Commun., Vol. 48, Issue 1
  • DOI: 10.1039/C1CC14731E

Magnetically Driven Ferroelectric Order in Ni 3 V 2 O 8
journal, August 2005


Classical spin and quantum-mechanical descriptions of geometric spin frustration
journal, July 2004

  • Dai, Dadi; Whangbo, Myung-Hwan
  • The Journal of Chemical Physics, Vol. 121, Issue 2
  • DOI: 10.1063/1.1760749

Influence of side groups on 90° superexchange: A modification of the Goodenough-Kanamori-Anderson rules
journal, August 1996


Highly efficient Nd:YVO 4 diode‐laser end‐pumped laser
journal, December 1987

  • Fields, R. A.; Birnbaum, M.; Fincher, C. L.
  • Applied Physics Letters, Vol. 51, Issue 23
  • DOI: 10.1063/1.98500

The hydrothermal synthesis, solubility and crystal growth of YVO4 and Nd:YVO4
journal, October 2008


Hydrothermal Synthesis and Comparative Coordination Chemistry of New Rare-Earth V 4+ Compounds
journal, March 2012

  • Kimani, Martin M.; McMillen, Colin D.; Kolis, Joseph W.
  • Inorganic Chemistry, Vol. 51, Issue 6
  • DOI: 10.1021/ic2024132

Structural and magnetic characterization of the one-dimensional S = 5 / 2 antiferromagnetic chain system SrMn ( V O 4 ) ( OH )
journal, June 2016

  • Sanjeewa, Liurukara D.; Garlea, Vasile O.; McGuire, Michael A.
  • Physical Review B, Vol. 93, Issue 22
  • DOI: 10.1103/PhysRevB.93.224407

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

Bond-valence parameters for solids
journal, April 1991

  • Brese, N. E.; O'Keeffe, M.
  • Acta Crystallographica Section B Structural Science, Vol. 47, Issue 2
  • DOI: 10.1107/S0108768190011041

Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database
journal, August 1985

  • Brown, I. D.; Altermatt, D.
  • Acta Crystallographica Section B Structural Science, Vol. 41, Issue 4
  • DOI: 10.1107/S0108768185002063

K2Mn3(OH)2(VO4)2, a New Two-Dimensional Potassium Manganese(II) Hydroxyvanadate
journal, February 1996

  • Liao, J. H.; Guyomard, D.; Piffard, Y.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 52, Issue 2
  • DOI: 10.1107/S0108270195010559

Ferrimagnetism of the Heisenberg Models on the Quasi-One-Dimensional Kagome Strip Lattices
journal, August 2012

  • Shimokawa, Tokuro; Nakano, Hiroki
  • Journal of the Physical Society of Japan, Vol. 81, Issue 8
  • DOI: 10.1143/JPSJ.81.084710

Dimanganese(II) hydroxide vanadate, Mn 2 (OH)[VO 4 ]
journal, June 2014

  • Sun, Kewen; Möller, Angela
  • Acta Crystallographica Section E Structure Reports Online, Vol. 70, Issue 7
  • DOI: 10.1107/S1600536814012926

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


The First Vanadate–Carbonate, K 2 Mn 3 (VO 4 ) 2 (CO 3 ): Crystal Structure and Physical Properties
journal, January 2013

  • Yakubovich, Olga V.; Yakovleva, Ekaterina V.; Golovanov, Alexey N.
  • Inorganic Chemistry, Vol. 52, Issue 3
  • DOI: 10.1021/ic302333e

A thermodynamic theory of “weak” ferromagnetism of antiferromagnetics
journal, January 1958


Anisotropic Superexchange Interaction and Weak Ferromagnetism
journal, October 1960


High-field multifrequency ESR in the S = 5 2 kagome-lattice antiferromagnet KFe 3 (OH) 6 (SO 4 ) 2
journal, March 2012


Symmetry breaking due to Dzyaloshinsky-Moriya interactions in the kagomé lattice
journal, July 2002


Observation of 1/3 Magnetization-Plateau-Like Anomaly in S =3/2 Perfect Kagomé Lattice Antiferromagnet KCr 3 (OH) 6 (SO 4 ) 2 (Cr-jarosite)
journal, June 2011

  • Okuta, Koji; Hara, Shigeo; Sato, Hirohiko
  • Journal of the Physical Society of Japan, Vol. 80, Issue 6
  • DOI: 10.1143/JPSJ.80.063703

Hydrogen bonding in selected vanadates: a Raman and infrared spectroscopy study
journal, August 2004

  • Frost, Ray L.; Erickson, Kristy L.; Weier, Matt L.
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 60, Issue 10
  • DOI: 10.1016/j.saa.2003.12.017

Raman and infrared spectroscopy of selected vanadates
journal, March 2005

  • Frost, Ray L.; Erickson, Kristy L.; Weier, Matt L.
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 61, Issue 5
  • DOI: 10.1016/j.saa.2004.06.006

    Works referencing / citing this record:

    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

    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

    PbFePO 4 F 2 with a 1/6th bond depleted triangular lattice
    journal, January 2018

    • Lu, Hongcheng; Kageyama, Hiroshi
    • Dalton Transactions, Vol. 47, Issue 43
    • DOI: 10.1039/c8dt03802c

    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

    • Smith Pellizzeri, Tiffany M.; Sanjeewa, Liurukara D.; Pellizzeri, Steven
    • Dalton Transactions, Vol. 49, Issue 14
    • DOI: 10.1039/c9dt03389k

    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

    Rechargeable potassium-ion batteries with honeycomb-layered tellurates as high voltage cathodes and fast potassium-ion conductors
    journal, September 2018


    The magnetic order of a manganese vanadate system with two-dimensional striped triangular lattice
    journal, October 2018

    • Garlea, V. Ovidiu; McGuire, Michael A.; Sanjeewa, Liurukara D.
    • AIP Advances, Vol. 8, Issue 10
    • DOI: 10.1063/1.5043124