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Open-Framework Manganese(II) and Cobalt(II) Borophosphates with Helical Chains: Structures, Magnetic, and Luminescent Properties
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Iowa State University, USA.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Iowa State University, USA; Wrocław Research Centre EIT+, Poland.
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Number of Authors: 7
2017 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 56, no 18, 11104-11112 p.Article in journal (Refereed) Published
Abstract [en]

Two borophosphates, (NH4)(1-2x)M1+x(H2O)(2)(BP2O8)center dot yH(2)O with M = Mn (I) and Co (II), synthesized hydrothermally crystallize in enantiomorphous space groups P6(5)22 and P6(1)22 with a = 9.6559(3) and 9.501(3) angstrom, c = 15.7939(6) and 15.582(4) angstrom, and V = 1275.3(1) and 1218.2(8) angstrom(3) 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 mu s 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.

Place, publisher, year, edition, pages
2017. Vol. 56, no 18, 11104-11112 p.
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Chemical Sciences
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URN: urn:nbn:se:su:diva-148088DOI: 10.1021/acs.inorgchem.7b01423ISI: 000411549400031PubMedID: 28862443OAI: oai:DiVA.org:su-148088DiVA: diva2:1151157
Available from: 2017-10-23 Created: 2017-10-23 Last updated: 2017-10-23Bibliographically approved

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Smetana, VolodymyrWilk-Kozubek, MagdalenaMudring, Anja-Verena
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