Lanthanide coordination polymers with tetrafluoroterephthalate as a bridging ligand: thermal and optical properties

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)(NO(3))(DMF)(2)]·DMF (Ln(3+) = 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 tfBDC(2-) 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 (BDC(2-)) as a bridging ligand; as for tfBDC(2-), a nonplanar conformation of the ligand is energetically more favorable, whereas for BDC(2-), 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 tfBDC(2-) ligand. The residues could not be identified. The emission spectra of the (∞)(2)[Ln(tfBDC)(NO(3))(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.