Department of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University, Tianjin 300071, PR China.
Chem Asian J. 2013 Jul;8(7):1412-8. doi: 10.1002/asia.201300250. Epub 2013 May 9.
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.
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。