Honeycomb-like S = 5/2 spin-lattices in manganese(II) vanadates

Liurukara D. Sanjeewa; Michael A. McGuire; Colin D. McMillen; Daniel Willett; George Chumanov; Joseph W. Kolis

doi:10.1021/acs.inorgchem.6b01286

Honeycomb-like S = 5/2 spin-lattices in manganese(II) vanadates

Liurukara D. Sanjeewa, Michael A. McGuire, Colin D. McMillen, Daniel Willett, George Chumanov, Joseph W. Kolis

Correlated Electron Materials

Research output: Contribution to journal › Article › peer-review

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Abstract

New complex manganese vanadate materials were synthesized as high-quality single crystals in multi-millimeter lengths using a high-temperature, highpressure hydrothermal method. One compound, Mn₅(VO₄)₂(OH)₄, was grown 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. Temperature-dependent magnetic studies indicated Curie-Weiss behavior above 100 K with significant antiferromagnetic 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.

Original language	English
Pages (from-to)	9240-9249
Number of pages	10
Journal	Inorganic Chemistry
Volume	55
Issue number	18
DOIs	https://doi.org/10.1021/acs.inorgchem.6b01286
State	Published - Sep 19 2016

Funding

The authors thank the National Science Foundation Grant No. DMR-1410727 for financial support. Work at Oak Ridge National Laboratory was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division (magnetic studies).

Funders	Funder number
National Science Foundation	DMR-1410727
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Division of Materials Sciences and Engineering

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10.1021/acs.inorgchem.6b01286

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@article{e38da554951948f699e6bf9e7040bb15,

title = "Honeycomb-like S = 5/2 spin-lattices in manganese(II) vanadates",

abstract = "New complex manganese vanadate materials were synthesized as high-quality single crystals in multi-millimeter lengths using a high-temperature, highpressure hydrothermal method. One compound, Mn5(VO4)2(OH)4, was grown 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) {\AA}, b = 9.5627(9) {\AA}, c = 5.4139(6) {\AA}, β = 98.529(8)°; Mn6O(VO4)2(OH): P21/m, Z = 2, a = 8.9363(12) {\AA}, b = 6.4678(8) {\AA}, c = 10.4478(13) {\AA}, 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. Temperature-dependent magnetic studies indicated Curie-Weiss behavior above 100 K with significant antiferromagnetic 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.",

author = "Sanjeewa, {Liurukara D.} and McGuire, {Michael A.} and McMillen, {Colin D.} and Daniel Willett and George Chumanov and Kolis, {Joseph W.}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = sep,

day = "19",

doi = "10.1021/acs.inorgchem.6b01286",

language = "English",

volume = "55",

pages = "9240--9249",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "18",

}

TY - JOUR

T1 - Honeycomb-like S = 5/2 spin-lattices in manganese(II) vanadates

AU - Sanjeewa, Liurukara D.

AU - McGuire, Michael A.

AU - McMillen, Colin D.

AU - Willett, Daniel

AU - Chumanov, George

AU - Kolis, Joseph W.

PY - 2016/9/19

Y1 - 2016/9/19

N2 - New complex manganese vanadate materials were synthesized as high-quality single crystals in multi-millimeter lengths using a high-temperature, highpressure hydrothermal method. One compound, Mn5(VO4)2(OH)4, was grown 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. Temperature-dependent magnetic studies indicated Curie-Weiss behavior above 100 K with significant antiferromagnetic 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.

AB - New complex manganese vanadate materials were synthesized as high-quality single crystals in multi-millimeter lengths using a high-temperature, highpressure hydrothermal method. One compound, Mn5(VO4)2(OH)4, was grown 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. Temperature-dependent magnetic studies indicated Curie-Weiss behavior above 100 K with significant antiferromagnetic 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.

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U2 - 10.1021/acs.inorgchem.6b01286

DO - 10.1021/acs.inorgchem.6b01286

M3 - Article

AN - SCOPUS:84988321904

SN - 0020-1669

VL - 55

SP - 9240

EP - 9249

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 18

ER -

Honeycomb-like S = 5/2 spin-lattices in manganese(II) vanadates

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