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

Dalton Transactions : an International Journal of Inorganic Chemistry
Miriam SobierayUwe Ruschewitz

Abstract

Ten new coordination polymers of the general compositions ∞²[Ln(III)(tfBDC)(NO3)(DMF)2]·DMF with Ln(III) = Eu(3+) (1), Gd(3+) (2), Tb(3+) (3), Ho(3+) (4), Tm(3+) (5), ∞²[Ln(III)(tfBDC)(CH3COO)(FA)3]·3FA with Ln(III) = Sm(3+) (6), Eu(3+) (7) and ∞²[Ln(III)(tfBDC)(NO3)(DMSO)2] with Ln(III) = Ho(3+) (8), Er(3+) (9) and Tm(3+) (10) were synthesized and structurally characterized by X-ray single crystal diffraction (tfBDC(2-) = 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 P1̄ 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 (tfBDC(2-)) 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...Continue Reading

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