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Open-Framework Manganese(II) and Cobalt(II) Borophosphates with Helical Chains: Structures, Magnetic, and Luminescent Properties

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Department of Chemistry, Iowa State University, Ames, Iowa 50011-3111, United States
Ames Laboratory, U.S. Department of Energy, Iowa State University, Ames, Iowa 50011-3020, United States
§ Department of Materials and Environmental Chemistry, Stockholm University, Svante Arrhenius väg 16 C, 10691 Stockholm, Sweden
Department of Materials Science and Engineering, Iowa State University, Ames, Iowa 50011-2300, United States
Department of Nanotechnology, Wrocław Research Centre EIT+, 147 Stabłowicka Street, 54-066 Wrocław, Poland
Cite this: Inorg. Chem. 2017, 56, 18, 11104–11112
Publication Date (Web):September 1, 2017
https://doi.org/10.1021/acs.inorgchem.7b01423
Copyright © 2017 American Chemical Society
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Abstract

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Two borophosphates, (NH4)1–2xM1+x(H2O)2(BP2O8yH2O with M = Mn (I) and Co (II), synthesized hydrothermally crystallize in enantiomorphous space groups P6522 and P6122 with a = 9.6559(3) and 9.501(3) Å, c = 15.7939(6) and 15.582(4) Å, and V = 1275.3(1) and 1218.2(8) Å3 for I and II, respectively. Both compounds feature helical chains composed of vertex-sharing tetrahedral PO4 and BO4 groups that are connected through O atoms to transition-metal cations, Mn2+ and Co2+, respectively. For the two crystallographically distinct transition-metal cation sites present in the structure, this results in octahedral coordination with different degrees of distortion from the ideal symmetry. The crystal-field parameters, calculated from the corresponding absorption spectra, indicate that Mn2+ and Co2+ ions are located in a weak octahedral-like crystal field and suggest that the Co–ligand interactions are more covalent than the Mn–ligand ones. Luminescence measurements at room temperature reveal an orange emission that red-shifts upon lowering of the temperature to 77 K for I, while II is not luminescent. The luminescence lifetimes of I are 33.4 μs at room temperature and 1.87 ms at 77 K. Both compounds are Curie–Weiss paramagnets with negative Weiss constants and effective magnetic moments expected for noninteracting Mn2+ and Co2+ cations but no clear long-range magnetic order above 2 K.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b01423.

  • Crystal photograph of II, powder XRD patterns, XPS, luminescence, IR, and Raman spectra for both compounds (PDF)

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CCDC 15517721551773 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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