Zhu Li-Na, Xu Na, Zhang Wei, Liao Dai-Zheng, Yoshimura Kazuyoshi, Mibu Ko, Jiang Zong-Hui, Yan Shi-Ping, Cheng Peng
Department of Chemistry, Nankai University, Tianjin 300071, China.
Inorg Chem. 2007 Feb 19;46(4):1297-304. doi: 10.1021/ic061792m. Epub 2007 Jan 23.
Four heteronuclear complexes Mn(CuL)2(SCN)2 (1), {[Mn(CuL)2(mu-dca)2].2H2O}n (2), Zn(CuL)2(SCN)2 (3), and [Fe(CuL)(N3)2]2 (4) incorporating macrocyclic oxamide ligands have been synthesized and structurally characterized. L is the dianion of diethyl 5,6,7,8,15,16-hexahydro-6,7-dioxodibenzo[1,4,8,11]-tetraazacyclotetradecine-13,18-dicarboxylate, and dca is the dicyanamide. The structure of 1 or 3 consists of oxamido-bridged trinuclear [MIICuII2] molecules (for 1, M is the manganese(II) ion, and for 3, M is the zinc(II) ion). Both of them consist of 1D supramolecuar chains via pi-pi interactions. The structure of 2 also has the oxamido-bridged trinuclear [MnIICuII2] structure units and consists of 2D layers formed by the linkage of copper(II) and manganese(II) atoms via the oxamido and mu1, 5-dca bridges. Complex 4 consists of oxamido-bridged tetranuclear [FeII2CuII2] molecules and arranges in 1D chains. Different co-ligands may result in different structures in this macrocyclic oxamide system. The variable-temperature magnetic susceptibility measurements (2-300 K) of 1 and 2 both show the pronounced antiferromagnetic interactions between the copper(II) and manganese(II) ions.
已合成并对四种包含大环草酰胺配体的异核配合物Mn(CuL)2(SCN)2 (1)、{[Mn(CuL)2(μ-dca)2].2H2O}n (2)、Zn(CuL)2(SCN)2 (3)和[Fe(CuL)(N3)2]2 (4)进行了结构表征。L是5,6,7,8,15,16-六氢-6,7-二氧代二苯并[1,4,8,11]-四氮杂环十四烷-13,18-二羧酸二乙酯的二价阴离子，dca是双氰胺。1或3的结构由草酰胺桥联的三核[MIICuII2]分子组成（对于1，M是锰(II)离子，对于3，M是锌(II)离子）。它们都通过π-π相互作用形成一维超分子链。2的结构也具有草酰胺桥联的三核[MnIICuII2]结构单元，由铜(II)和锰(II)原子通过草酰胺和μ1,5-dca桥连接形成二维层。配合物4由草酰胺桥联的四核[FeII2CuII2]分子组成并排列成一维链。在这个大环草酰胺体系中，不同的共配体可能导致不同的结构。1和2的变温磁化率测量（2 - 300 K）均显示铜(II)和锰(II)离子之间存在明显的反铁磁相互作用。
