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Crystal Structures and Effect of Temperature on the Luminescence of Two Lanthanide Coordination Polymers with Twofold Interpenetrating pcu Topology

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Abstract

Two new lanthanide coordination polymers formulated as [Ln(BDC)1.5(DMF)(H2O)] n [Ln = Tb (1), Gd (2)] [H2BDC = 1,4-benzenedicarboxylic acid, DMF = N,N′-dimethylformamide] were synthesized under solvothermal conditions. The coordination polymers were characterized by IR spectroscopy, elemental analysis and X-ray single-crystal diffraction. The two coordination polymers are isostructural and exhibit twofold interpenetrating pcu three-dimensional open frameworks constructed by tetradentate ligand of H2BDC. The fluorescence properties of 1 and 2 were investigated at 298 or 77 K both in solid state and in CH2Cl2 solvent dispersed as suspensions. Coordination polymer 1 exhibits characteristic Tb3+ ions emission transitions of 5D4 → 7F J (J = 6–2) at 77 or 298 K both in the solid-state and in CH2Cl2 solvent. Moreover, the vibrational structure of 1 is more defined at 77 K, which exhibits another two 5D4 → 7F1 and 5D4 → 7F2 transitions more than that at 298 K. The lifetimes of 1 are longer at 77 K (915.2 μs in the solid state and 874.11 μs in the CH2Cl2 solvent) than that at 298 K (866.31 μs in the solid state and 801.04 μs in the CH2Cl2 solvent), which may be caused by the increase of radiative rate and decrease of non-radiative rate at low temperature. The singlet excited state (28,653 cm−1) and the lowest triplet energy level (23,641 cm−1) of H2BDC ligand were calculated based on the UV–Vis absorbance edges of ligand and the phosphorescence spectrum of Gd3+ coordination polymer (2) at 77 K, showing that the effective extent of energy transfer from H2BDC ligand to Tb3+ ion. Finally, thermal behaviors of the two coordination polymers were studied by thermogravimetric analysis, which exhibit thermal stability to 250 °C.

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant Nos. 21371040 and 21171044), the National key Basic Research Program of China (973 Program, No. 2013CB632900), and supported by Program for Innovation Research of Science in Harbin Institute of Technology.

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  1. Department of Chemistry, Harbin Institute of Technology, Harbin, 150001, People’s Republic of China

    Hui-Jie Zhang, Rui-Qing Fan, Ping Wang, Xin-Ming Wang, Wei Chen, Xu-Bin Zheng, Kai Li & Yu-Lin Yang

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  1. Hui-Jie Zhang
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Correspondence to Rui-Qing Fan.

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Zhang, HJ., Fan, RQ., Wang, P. et al. Crystal Structures and Effect of Temperature on the Luminescence of Two Lanthanide Coordination Polymers with Twofold Interpenetrating pcu Topology. J Inorg Organomet Polym 24, 624–632 (2014). https://doi.org/10.1007/s10904-014-0025-0

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