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Issue 13, 2015
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Bright luminescence in lanthanide coordination polymers with tetrafluoroterephthalate as a bridging ligand

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Abstract

Ten new coordination polymers of the general compositions 2[LnIII(tfBDC)(NO3)(DMF)2]·DMF with LnIII = Eu3+ (1), Gd3+ (2), Tb3+ (3), Ho3+ (4), Tm3+ (5), 2[LnIII(tfBDC)(CH3COO)(FA)3]·3FA with LnIII = Sm3+ (6), Eu3+ (7) and 2[LnIII(tfBDC)(NO3)(DMSO)2] with LnIII = Ho3+ (8), Er3+ (9) and Tm3+ (10) were synthesized and structurally characterized by X-ray single crystal diffraction (tfBDC2− = 2,3,5,6-tetrafluoroterephthalate, DMF = N,N′-dimethylformamide, FA = formamide, DMSO = dimethyl sulfoxide). 1–5 crystallize in the monoclinic space group C2/c with Z = 8, 6 and 7 in P[1 with combining macron] with Z = 2 and 8–10 in Pbca with Z = 8. All crystal structures contain binuclear lanthanide nodes that are connected by 2,3,5,6-tetrafluoroterephthalates (tfBDC2−) to form two-dimensional polymeric structural units. Despite this common structural feature the coordination within these binuclear units is quite different in detail, e.g. CN = 9 for 1–7 and CN = 8 for 8–10. The emission spectra of the europium (1, 7) and terbium (3) compounds reveal bright red and green emission in the visible region. The resulting high quantum yields of 53% (1) and 67% (3) at room temperature show that the replacement of organic ligands with C–H groups by perfluorinated ligands leads to compounds with intense emission, as vibrational quenching is reduced. On the other hand, the influence of the coordinating solvent and additional ligands cannot be neglected, as the replacement of DMF by FA and NO3 by CH3COO in 7 leads to a reduced quantum yield of only 10%. Thermoanalytical investigations show that all compounds are stable up to 100–150 °C, before a stepwise release of solvent molecules starts followed by a decomposition of the coordination polymer.

Graphical abstract: Bright luminescence in lanthanide coordination polymers with tetrafluoroterephthalate as a bridging ligand

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Publication details

The article was received on 05 Dec 2014, accepted on 19 Feb 2015 and first published on 23 Feb 2015


Article type: Paper
DOI: 10.1039/C4DT03733B
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2015,44, 6249-6259
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    Bright luminescence in lanthanide coordination polymers with tetrafluoroterephthalate as a bridging ligand

    M. Sobieray, J. Gode, C. Seidel, M. Poß, C. Feldmann and U. Ruschewitz, Dalton Trans., 2015, 44, 6249
    DOI: 10.1039/C4DT03733B

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