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Title: Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties

Abstract

In this study, two new halide-containing cesium manganese vanadates have been synthesized by a high-temperature (580 °C) hydrothermal synthetic method from aqueous brine solutions. One compound, Cs 3Mn(VO 3) 4Cl, (1) was prepared using a mixed cesium hydroxide/chloride mineralizer, and crystallizes in the polar noncentrosymmetric space group Cmm2, with a = 16.7820(8) Å, b = 8.4765(4) Å, c = 5.7867(3) Å. This structure is built from sinusoidal zig-zag (VO 3) n chains that run along the b-axis and are coordinated to Mn 2+ containing (MnO 4Cl) square-pyramidal units that are linked together to form layers. The cesium cations reside between the layers, but also coordinate to the chloride ion, forming a cesium chloride chain that also propagates along the b-axis. The other compound, Cs 2Mn(VO 3) 3F, (2) crystallizes in space group Pbca with a = 7.4286(2) Å, b = 15.0175(5) Å, c = 19.6957(7) Å, and was prepared using a cesium fluoride mineralizer. The structure is comprised of corner sharing octahedral Mn 2+ chains, with trans fluoride ligands acting as bridging units, whose ends are capped by (VO 3) n vanadate chains to form slabs. The cesium atoms reside between the manganese vanadate layers, and also play an integralmore » part in the structure, forming a cesium fluoride chain that runs along the b-axis. Both compounds were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and single-crystal Raman spectroscopy. Additionally, the magnetic properties of 2 were investigated. Lastly, above 50 K, it displays behavior typical of a low dimensional system with antiferromagnetic interactions, as to be expected for linear chains of manganese(II) within the crystal structure.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1];  [1];  [1];  [1]
  1. Clemson Univ., SC (United States). Department of Chemistry and Center for Optical Materials Science and Engineering Technologies (COMSET)
  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) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1422572
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 47; Journal Issue: 8; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hydrothermal; crystal growth; vanadate; cesium vanadates; transition metal; halide-containing

Citation Formats

Smith Pellizzeri, Tiffany M., McGuire, Michael A., McMillen, Colin D., Wen, Yimei, Chumanov, George, and Kolis, Joseph W. Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties. United States: N. p., 2018. Web. doi:10.1039/c7dt04642a.
Smith Pellizzeri, Tiffany M., McGuire, Michael A., McMillen, Colin D., Wen, Yimei, Chumanov, George, & Kolis, Joseph W. Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties. United States. doi:10.1039/c7dt04642a.
Smith Pellizzeri, Tiffany M., McGuire, Michael A., McMillen, Colin D., Wen, Yimei, Chumanov, George, and Kolis, Joseph W. Wed . "Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties". United States. doi:10.1039/c7dt04642a. https://www.osti.gov/servlets/purl/1422572.
@article{osti_1422572,
title = {Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties},
author = {Smith Pellizzeri, Tiffany M. and McGuire, Michael A. and McMillen, Colin D. and Wen, Yimei and Chumanov, George and Kolis, Joseph W.},
abstractNote = {In this study, two new halide-containing cesium manganese vanadates have been synthesized by a high-temperature (580 °C) hydrothermal synthetic method from aqueous brine solutions. One compound, Cs3Mn(VO3)4Cl, (1) was prepared using a mixed cesium hydroxide/chloride mineralizer, and crystallizes in the polar noncentrosymmetric space group Cmm2, with a = 16.7820(8) Å, b = 8.4765(4) Å, c = 5.7867(3) Å. This structure is built from sinusoidal zig-zag (VO3)n chains that run along the b-axis and are coordinated to Mn2+ containing (MnO4Cl) square-pyramidal units that are linked together to form layers. The cesium cations reside between the layers, but also coordinate to the chloride ion, forming a cesium chloride chain that also propagates along the b-axis. The other compound, Cs2Mn(VO3)3F, (2) crystallizes in space group Pbca with a = 7.4286(2) Å, b = 15.0175(5) Å, c = 19.6957(7) Å, and was prepared using a cesium fluoride mineralizer. The structure is comprised of corner sharing octahedral Mn2+ chains, with trans fluoride ligands acting as bridging units, whose ends are capped by (VO3)n vanadate chains to form slabs. The cesium atoms reside between the manganese vanadate layers, and also play an integral part in the structure, forming a cesium fluoride chain that runs along the b-axis. Both compounds were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and single-crystal Raman spectroscopy. Additionally, the magnetic properties of 2 were investigated. Lastly, above 50 K, it displays behavior typical of a low dimensional system with antiferromagnetic interactions, as to be expected for linear chains of manganese(II) within the crystal structure.},
doi = {10.1039/c7dt04642a},
journal = {Dalton Transactions},
number = 8,
volume = 47,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Table 1 Table 1: Crystallographic data of Cs3Mn(VO3)4Cl (1) and Cs2Mn(VO3)3F (2).

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    Chlorovanadates with Original Chain and Layered Structures: AVO3Cl (A=Ba, Sr, Cd)
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    Hydrothermal synthesis of single crystals of transition metal vanadates in the glaserite phase
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    • Chirayil, Thomas; Zavalij, Peter Y.; Whittingham, M. Stanley
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    journal, December 2013

    • Holland, Michael; Donakowski, Martin D.; Pozzi, Eric A.
    • Inorganic Chemistry, Vol. 53, Issue 1
    • DOI: 10.1021/ic402177j

    Multidimensional Open-Frameworks: Combinations of One-Dimensional Channels and Two-Dimensional Layers in Novel Bi/M Oxo-Chlorides
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    • Lü, Minfeng; Aliev, Almaz; Olchowka, Jacob
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    • DOI: 10.1021/ic402578m

    On the Origin of the Differences in Structure Directing Properties of Polar Metal Oxyfluoride [MO x F 6– x ] 2– ( x = 1, 2) Building Units
    journal, January 2015

    • Gautier, Romain; Gautier, Régis; Chang, Kelvin B.
    • Inorganic Chemistry, Vol. 54, Issue 4
    • DOI: 10.1021/ic5026735

    Flux Synthesis, Crystal Structures, and Luminescence Properties of Salt-Inclusion Lanthanide Silicates: [K 9 F 2 ][Ln 3 Si 12 O 32 ] (Ln = Sm, Eu, Gd)
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    • Tang, Ming-Feng; Chiang, Pei-Yun; Su, Yu-Han
    • Inorganic Chemistry, Vol. 47, Issue 19
    • DOI: 10.1021/ic801007k

    Fluoride-Rich, Hydrofluorothermal Routes to Functional Transition Metal (Mn, Fe, Co, Cu) Fluorophosphates
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    Ore-Forming Fluids
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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.