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Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux

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    Article

    Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux
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    • Vladislav V. Klepov
      Vladislav V. Klepov
      Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
      More by Vladislav V. Klepov
      Orcidhttp://orcid.org/0000-0002-2039-2457
    • Logan S. Breton
      Logan S. Breton
      Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
      More by Logan S. Breton
    • Kristen A. Pace
      Kristen A. Pace
      Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
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    • Vancho Kocevski
      Vancho Kocevski
      Department of Mechanical Engineering, University of South Carolina, Columbia, South Carolina 29208, United States
      More by Vancho Kocevski
      Orcidhttp://orcid.org/0000-0002-2127-5834
    • Theodore M. Besmann
      Theodore M. Besmann
      Department of Mechanical Engineering, University of South Carolina, Columbia, South Carolina 29208, United States
      More by Theodore M. Besmann
    • Hans-Conrad zur Loye*
      Hans-Conrad zur Loye
      Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
      *E-mail: [email protected]
      More by Hans-Conrad zur Loye
      Orcidhttp://orcid.org/0000-0001-7351-9098
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2019, 58, 9, 6565–6573
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    https://doi.org/10.1021/acs.inorgchem.9b00806
    Published April 23, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    To determine the influence of the lanthanide size on the structures and properties of thiophosphates, a thiophosphate series containing different lanthanides was synthesized via high temperature flux crystal growth and their structures and physical properties analyzed and compared. Layered thiohypophosphates NaLnP2S6 (Ln = La, Ce, Pr) and thiopyrophosphates CsLnP2S7 (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Yb, Y) were grown out of an iodide flux using consistent reaction conditions across both series. Under the mildly reducing iodide flux reaction conditions, a rather rare example of phosphorus reduction from the +5 to the +4 oxidation state was observed. Both resultant structure types are based on lanthanide thiophosphate sheets with the alkali cations located between them. Magnetic susceptibility measurements were conducted and revealed Curie–Weiss behavior of the samples, with a Van Vleck contribution in the CsSmP2S7 sample. UV–vis data was found to be in good agreement with the literature, indicating little influence of the sulfide environment on the localized 4f orbitals.

    Copyright © 2019 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b00806.

    • PXRD patterns, UV–vis spectra, EDS results, and magnetic susceptibility versus temperature plots (PDF)

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    CCDC 1891155–1891166 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    This article is cited by 23 publications.

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    15. Zi-Xia Chen, Wenlong Liu, Sheng-Ping Guo. A review of structures and physical properties of rare earth chalcophosphates. Coordination Chemistry Reviews 2023, 474 , 214870. https://doi.org/10.1016/j.ccr.2022.214870
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    17. Pia L. Lange, Thomas Schleid. Li 3 La[PS 4 ] 2 : The First Lithium Lanthanum Ortho ‐Thiophosphate. European Journal of Inorganic Chemistry 2021, 2021 (32) , 3247-3254. https://doi.org/10.1002/ejic.202100386
    18. Logan S. Breton, Mark D. Smith, Hans-Conrad zur Loye. Trends in rare earth thiophosphate syntheses: Rb 3 Ln(PS 4 ) 2 (Ln = La, Ce, Pr), Rb 3−x Na x Ln(PS 4 ) 2 (Ln = Ce, Pr; x = 0.50, 0.55), and RbEuPS 4 obtained by molten flux crystal growth. CrystEngComm 2021, 23 (30) , 5241-5248. https://doi.org/10.1039/D1CE00703C
    19. Pia L. Lange, Thomas Schleid. Li 9 Yb 2 [PS 4 ] 5 and Li 6 Yb 3 [PS 4 ] 5 : two lithium-containing ytterbium(III) thiophosphates(V) revisited. Zeitschrift für Naturforschung B 2021, 76 (5) , 281-291. https://doi.org/10.1515/znb-2021-0023
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2019, 58, 9, 6565–6573
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.9b00806
    Published April 23, 2019
    Copyright © 2019 American Chemical Society
    Request reuse permissions

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