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Lanthanide Coordination Polymers with Tetrafluoroterephthalate as a Bridging Ligand: Thermal and Optical Properties

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    Lanthanide Coordination Polymers with Tetrafluoroterephthalate as a Bridging Ligand: Thermal and Optical Properties
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    † Department of Chemistry, University of Cologne, Greinstraße 6, D-50939 Cologne, Germany
    ‡ Anorganische Chemie I − Festkörperchemie und Materialien, Ruhr-Universität Bochum, D-44801 Bochum, Germany
    *Phone: (+49)221-470-3285. Fax: (+49)221-470-3933. E-mail addresses: [email protected] (A.-V.M.), [email protected](U.R.).
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2012, 51, 8, 4679–4688
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    https://doi.org/10.1021/ic202655d
    Published March 23, 2012
    Copyright © 2012 American Chemical Society
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    Abstract

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    By slow diffusion of triethylamine into a solution of 2,3,5,6-tetrafluoroterephthalic acid (H2tfBDC) and the respective lanthanide salt in EtOH/DMF single crystals of seven nonporous coordination polymers, ∞2[Ln(tfBDC)(NO3)(DMF)2]·DMF (Ln3+ = Ce, Pr, Nd, Sm, Dy, Er, Yb; C2/c, Z = 8) have been obtained. In the crystal structures, two-dimensional square grids are found, which are composed of binuclear lanthanide nodes connected by tfBDC2– as a linking ligand. The coordination sphere of each lanthanide cation is completed by a nitrate anion and two DMF molecules (CN = 9). This crystal structure is unprecedented in the crystal chemistry of coordination polymers based on nonfluorinated terephthalate (BDC2–) as a bridging ligand; as for tfBDC2–, a nonplanar conformation of the ligand is energetically more favorable, whereas for BDC2–, a planar conformation is preferred. Differential thermal analysis/thermogravimetric analysis (DTA/TGA) investigations reveal that the noncoordinating DMF molecule is released first at temperatures of 100–200 °C. Subsequent endothermal weight losses correspond to the release of the coordinating DMF molecules. Between 350 and 400 °C, a strong exothermal weight loss is found, which is probably due to a decomposition of the tfBDC2– ligand. The residues could not be identified. The emission spectra of the ∞2[Ln(tfBDC)(NO3)(DMF)2]·DMF compounds reveal intense emission in the visible region of light for Pr, Sm, and Dy with colors from orange, orange-red, to warm white.

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    Experimental and simulated powder X-ray diffraction patterns, DTA/TG diagrams, IR spectra and X-ray crystallographic files in CIF format of compounds 1–7. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2012, 51, 8, 4679–4688
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    https://doi.org/10.1021/ic202655d
    Published March 23, 2012
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