Zhang Jian-Jun, Sheng Tian-Lu, Hu Sheng-Min, Xia Sheng-Qing, Leibeling Guido, Meyer Franc, Fu Zhi-Yong, Chen Ling, Fu Rui-Biao, Wu Xin-Tao
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China.
Chemistry. 2004 Aug 20;10(16):3963-9. doi: 10.1002/chem.200400018.
The first successful attempt to construct 3D supramolecular frameworks with high-nuclear 3d-4f heterometallic clusters as a node is reported. The self-assembly of Ln3+, Cu2+ and amino acid in solution leads to the formation of two polymers, 35-nuclear complex [Sm6Cu29] 1 with a primitive cubic net-like structure and 36-nuclear complex [Nd6Cu30] 2 with a face-centred cubic network type structure. Glycine and L-proline, respectively, were used as ligands. It should be noted that 2 has a chiral framework. X-ray structure analyses show that 1 crystallizes in the triclinic P1 space group (a=19.6451(8), b=20.4682(8), c=20.7046(8) A, alpha=89.453(1), beta=66.290(1), gamma=68.572(1) degrees, V=7003.0(5) A3 and Z=1) and 2 belongs to the cubic P2(1)3 space group (a=b=c=32.4341(3) A, V=34 119.7(5) A3 and Z=4). Both complexes utilize Ln6Cu24 octahedral clusters as nodes and trans-Cu(amino acid)2 groups as bridges. Electrical conductivity measurements reveal that both polymers behave as semiconductors.
报道了首次成功尝试构建以高核3d-4f异金属簇为节点的3D超分子框架。Ln3+、Cu2+和氨基酸在溶液中的自组装导致形成两种聚合物，具有原始立方网状结构的35核配合物[Sm6Cu29] 1和具有面心立方网络型结构的36核配合物[Nd6Cu30] 2。分别使用甘氨酸和L-脯氨酸作为配体。需要注意的是，2具有手性框架。X射线结构分析表明，1结晶于三斜P1空间群（a=19.6451(8)，b=20.4682(8)，c=20.7046(8) Å，α=89.453(1)，β=66.290(1)，γ=68.572(1)°，V=7003.0(5) Å3且Z=1），2属于立方P2(1)3空间群（a=b=c=32.4341(3) Å，V=34 119.7(5) Å3且Z=4）。两种配合物均以Ln6Cu24八面体簇为节点，以反式Cu(氨基酸)2基团为桥。电导率测量表明，两种聚合物均表现为半导体。
