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具有类沸石拓扑结构的新型镧系金属有机框架的合成、结构以及发光和磁性性质

Synthesis, structure, and luminescent and magnetic properties of novel lanthanide metal-organic frameworks with zeolite-like topology.

作者信息

Li Zhongyue, Zhu Guangshan, Guo Xiaodan, Zhao Xiaojun, Jin Zhao, Qiu Shilun

机构信息

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, China.

出版信息

Inorg Chem. 2007 Jun 25;46(13):5174-8. doi: 10.1021/ic061666i. Epub 2007 May 19.

Abstract

A series of microporous lanthanide metal-organic frameworks [Ln(BTC)(DMF)(2) x H(2)O, Ln = Tb (1), Dy (2), Ho (3), Er (4), Tm (5), Yb (6); DMF = N,N'-dimethylformamide] with 4 x 4 x 4 x 6 x 6 x 8 topology, which is very common in the zeolite topologies, have been synthesized under mild conditions. The single-crystal X-ray diffraction analysis reveals that they exhibit the same three-dimensional (3D) architecture and crystallize in monoclinic symmetry space group C2/c. Organic and inorganic four-connected nodes link each other to form a 3D open framework. The framework contains approximate 13 Angstrom x 7 Angstrom rectangle channels along the [1,1,0] and [1,-1,0] directions, respectively. The luminescent properties of these complexes have been studied, and complex 1 shows a Tb(3+) characteristic emission in the range of 450-650 nm at room temperature. Complexes 1-5 exhibit antiferromagnetic interaction between Ln(3+) ions. The water sorption isotherm shows that about 15 water molecules per unit cell can be adsorbed into the micropores of dehydrated complex 4.

摘要

一系列具有4×4×4×6×6×8拓扑结构(这种拓扑结构在沸石拓扑结构中非常常见)的微孔镧系金属有机框架化合物[Ln(BTC)(DMF)(2)·xH₂O,Ln = Tb (1),Dy (2),Ho (3),Er (4),Tm (5),Yb (6);DMF = N,N'-二甲基甲酰胺]已在温和条件下合成。单晶X射线衍射分析表明它们呈现相同的三维(3D)结构,且结晶于单斜对称空间群C2/c中。有机和无机的四连接节点相互连接形成一个3D开放框架。该框架分别沿[1,1,0]和[1,-1,0]方向包含近似13埃×7埃的矩形通道。已研究了这些配合物的发光性质,配合物1在室温下于450 - 650 nm范围内呈现Tb(3+)特征发射。配合物1 - 5在Ln(3+)离子之间表现出反铁磁相互作用。水吸附等温线表明,脱水后的配合物4的微孔中每单位晶胞可吸附约15个水分子。

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