title: Synthesis, structure, and luminescent properties of microporous lanthanide metal-organic frameworks with inorganic rod-shaped building units.
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.
authors.affiliation: State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, Jilin University, Changchun 130012, China.
authors.forename: Xiaodan
authors.initials: X
authors.lastname: Guo
authors.forename: Guangshan
authors.initials: G
authors.lastname: Zhu
authors.forename: Fuxing
authors.initials: F
authors.lastname: Sun
authors.forename: Zhongyue
authors.initials: Z
authors.lastname: Li
authors.forename: Xiaojun
authors.initials: X
authors.lastname: Zhao
authors.forename: Xiaotian
authors.initials: X
authors.lastname: Li
authors.forename: Hanchang
authors.initials: H
authors.lastname: Wang
authors.forename: Shilun
authors.initials: S
authors.lastname: Qiu