Synthesis, structure, and luminescent properties of microporous lanthanide metal-organic frameworks with inorganic rod-shaped building units

Inorganic Chemistry
Xiaodan GuoShilun Qiu

Abstract

A series of microporous lanthanide metal-organic frameworks, Tb3(BDC)(4.5)(DMF)2(H2O)3.(DMF)(H2O) (1) and Ln3(BDC)(4.5)(DMF)2(H2O)3.(DMF)(C2H5OH)(0.5)(H2O)(0.5) [Ln = Dy (2), Ho (3), Er (4)], have been synthesized by the reaction of the lanthanide metal ion (Ln3+) with 1,4-benzenedicarboxylic acid and triethylenetetramine in a mixed solution of N,N'-dimethylformamide (DMF), water, and C(2)H(5)OH. X-ray diffraction analyses reveal that they are extremely similar in structure and crystallized in triclinic space group P. An edge-sharing metallic dimer and 4 metallic monomers assemble with 18 carboxylate groups to form discrete inorganic rod-shaped building units [Ln6(CO2)18], which link to each other through phenyl groups to lead to three-dimensional open frameworks with approximately 4 x 6 A rhombic channels along the [0,-1,1] direction. A water sorption isotherm proves that guest molecules in the framework of complex 1 can be removed to create permanent microporosity and about four water molecules per formula unit can be adsorbed into the micropores. These complexes exhibit blue fluorescence, and complex 1 shows a Tb3+ characteristic emission in the range of 450-650 nm.

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Citations

Jun 22, 2011·Chemical Reviews·Yuanjing CuiBanglin Chen
Nov 16, 2011·Inorganic Chemistry·Asamanjoy BhuniaPeter W Roesky
May 2, 2007·Chemical Society Reviews·Daniel MaspochJaume Veciana
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Oct 5, 2010·Chemical Communications : Chem Comm·Zhao JinGuang-Shan Zhu
Nov 28, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Clément FalaiseThierry Loiseau
Apr 29, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Xin WangSu Jing
Sep 11, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Qiaozhen SunChunying Duan
Sep 26, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiao-Ping YangRachel Pen-jen Lai
Mar 26, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Zheng-Shuai BaiNorikazu Ueyama
Dec 22, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Xiaoping YangWai-Kwok Wong
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