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Lanthanide coordination polymers with tetrafluoroterephthalate as a bridging ligand: thermal and optical properties.
Autorzy
Rok wydania
2012
Czasopismo
Numer woluminu
51
Strony
4679-4688
DOI
10.1021/ic202655d
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
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.
Adres publiczny
https://doi.org/10.1021/ic202655d
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