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Near-Infrared Luminescence and Inner Filter Effects of Lanthanide Coordination Polymers with 1,2-Di(4-pyridyl)ethylene

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    Near-Infrared Luminescence and Inner Filter Effects of Lanthanide Coordination Polymers with 1,2-Di(4-pyridyl)ethylene
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    † †Institut für Anorganische Chemie and ‡Institut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
    *E-mail: [email protected]. Fax: (+)49-931-3184785. Phone: (+)49-931-3188724.
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2016, 55, 15, 7396–7406
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    https://doi.org/10.1021/acs.inorgchem.6b00447
    Published July 11, 2016
    Copyright © 2016 American Chemical Society
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    Abstract

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    A series of 12 lanthanide coordination polymers was synthesized from anhydrous LnCl3 and 1,2-di(4-pyridyl)ethylene (dpe) under solvothermal conditions in either thiazole (thz) or pyridine (py). The reactions yielded ∞1[Ln2Cl6(dpe)2(thz)4]·dpe with Ln = Ce (1), Nd (2), ∞1[LnCl3 (dpe)(py)2]·(dpe/py) with Ln = Gd (3), Er (4), and ∞1[LnCl3(dpe) (thz)2](dpe/thz) with Ln = Sm (5), Gd (6), Tb (7), Dy (8), Er (9), Yb (10), as well as ∞1[HoCl3(dpe)(thz)2]·thz (11) and ∞2[La2Cl6(dpe)3(py)2]·dpe (12). One-dimensional coordination polymers (CPs) and a two-dimensional network of five different constitutions are formed by connection of LnCl3 units via dpe molecules. As free ligand, dpe shows an excimer effect that is reduced in the coordination polymers. In addition, dipyridylethylene proves to be a suitable sensitizer for the photoluminescence of lanthanides in the near-infrared region (NIR) only. Thereby, dpe differs from the related ligand 1,2-di(4-pyridyl)ethane. For the compounds presented, four different luminescence effects were detected: luminescence based on fluorescence of the linker dpe is observed in the visible region, whereas ligand-sensitized 4f–4f NIR emission is dominating for trivalent Nd, Er, and Yb. The Er-containing CPs show an inner-filter effect of Er3+, which is based on reabsorption of emission of dpe triggering the erbium NIR emission.

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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.6b00447. Further information was deposited at the Cambridge Crystallographic Data Centre, CCDC, 12 Union Road, Cambridge CB2 1EZ, U.K. (e-mail: [email protected]) and may be requested by citing the deposition numbers CCDC Nd (2) 1414645, Gd (3) 1023748, Sm (5) 1414642, Dy (8) 1414641, Yb (10) 1414643, Ho (11) 1414644, and La (12) 1023749, or the names of the authors and the literature citation.

    • Additional crystal structure information, figures, selected interatomic distances and angles, excitation spectra, luminescence decay times, additional spectroscopic and thermal investigations. (PDF)

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2016, 55, 15, 7396–7406
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.6b00447
    Published July 11, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

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