Zhang Jian-Jun, Sheng Tian-Lu, Xia Sheng-Qin, Leibeling Guido, Meyer Franc, Hu Sheng-Min, Fu Rui-Biao, Xiang Sheng-Chang, 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.
Inorg Chem. 2004 Aug 23;43(17):5472-8. doi: 10.1021/ic0497073.
With glycine or L-alanine as ligands, a series of novel 3d-4f heterometallic Ln(6)Cu(24) clusters with the formulas of [Sm(6)Cu(24)(mu(3)-OH)(30)(Gly)(12)(Ac)(12)(ClO(4))(H(2)O)(16)].(ClO(4))(9).(OH)(2).(H(2)O)(31) (1) and [Ln(6)Cu(24)(mu(3)-OH)(30)(Ala)(12)(Ac)(6)(ClO(4))(H(2)O)(12)].(ClO(4))(10).(OH)(7).(H(2)O)(34) (2.Ln) (Ln = Tb, Gd, Sm, and La) were synthesized by self-assembly, among which 1 and 2.Tb were characterized by X-ray structure analysis. The metal skeleton of the clusters may be described as a huge [Ln(6)Cu(12)] octahedron (constructed with 6 Ln(III) ions located at the vertices and 12 inner Cu(II) ions located at the midpoints of the edges) connected by 12 additional Cu(II) ions (every 2 are connected to 1 Ln(III) vertex). The temperature dependence of the magnetic susceptibilities of 2.Ln was investigated and was found to vary with the central rare-earth ions. Impedance spectroscopic measurements of 2.Ln reveal that they are ionic conductors.
以甘氨酸或L-丙氨酸为配体，通过自组装合成了一系列化学式为[Sm₆Cu₂₄(μ₃-OH)₃₀(Gly)₁₂(Ac)₁₂(ClO₄)(H₂O)₁₆].(ClO₄)₉.(OH)₂.(H₂O)₃₁ (1) 和[Ln₆Cu₂₄(μ₃-OH)₃₀(Ala)₁₂(Ac)₆(ClO₄)(H₂O)₁₂].(ClO₄)₁₀.(OH)₇.(H₂O)₃₄ (2.Ln)（Ln = Tb、Gd、Sm和La）的新型3d-4f异金属Ln₆Cu₂₄簇合物，其中1和2.Tb通过X射线结构分析进行了表征。簇合物的金属骨架可描述为一个巨大的[Ln₆Cu₁₂]八面体（由位于顶点的6个Ln(III)离子和位于棱中点的12个内部Cu(II)离子构成），由另外12个Cu(II)离子连接（每2个连接到1个Ln(III)顶点）。研究了2.Ln的磁化率随温度的变化，发现其随中心稀土离子而变化。对2.Ln的阻抗谱测量表明它们是离子导体。
