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两个基于{OLn6 }簇的镧系(III)-铜(II)有机框架,表现出较大的磁热效应和磁化弛豫缓慢。

Two lanthanide(III)-copper(II) organic frameworks based on {OLn6 } clusters that exhibited a large magnetocaloric effect and slow relaxation of the magnetization.

机构信息

Department of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University, Tianjin 300071, PR China.

出版信息

Chem Asian J. 2013 Jul;8(7):1412-8. doi: 10.1002/asia.201300250. Epub 2013 May 9.

Abstract

Two new 3D lanthanide(III)-copper(II) organic frameworks based on unusual {OLn6} clusters have been successfully synthesized and fully characterized. Crystallographic studies showed that the {OLn6} clusters acted as 12-connected nodes that were linked together by [CuL2] (H2L = 3-hydroxypyrazine-2-carboxylic acid) moieties to construct an interesting 4,12-c net with the point symbol {4(36).6(30)}{4(4).6(2)}3. Magnetic studies revealed that these two isostructural heterometallic frameworks exhibited different magnetic properties, depending on the different anisotropies of the lanthanide spin carriers: Gd-Cu showed a large magnetocaloric effect, with an entropy change (-ΔS(m)) of 35.76 J  kg(-1)  K(-1), which is one of the largest values in high-dimensional complexes, whilst Dy-Cu exhibited slow relaxation of the magnetization at low temperatures.

摘要

两个新的基于不寻常的{OLn6}簇的三维镧系(III)-铜(II)有机框架已经被成功合成并进行了全面的表征。晶体学研究表明,{OLn6}簇作为 12 连接的节点,通过[CuL2](H2L=3-羟基吡嗪-2-羧酸)部分连接在一起,构建了一个有趣的具有点符号{4(36).6(30)}{4(4).6(2)}3 的 4,12-c 网络。磁性研究表明,这两个同构的杂金属框架表现出不同的磁性性质,这取决于镧系自旋载体的不同各向异性:Gd-Cu 表现出较大的磁热效应,熵变化(-ΔS(m))为 35.76 J kg(-1) K(-1),这是在高维配合物中最大的值之一,而 Dy-Cu 在低温下表现出缓慢的磁化弛豫。

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