Isostructural coordination capsules for a series of 10 different d5-d10 transition-metal ions
Isostructural coordination capsules for a series of 10 different d5-d10 transition-metal ions
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DOI：
10.1002/anie.200601431
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发表时间：
2006-01-01
影响因子：
16.6
通讯作者：
Shionoya, Mitsuhiko
中科院分区：
文献类型：
--
作者：
Hiraoka, Shuichi;Harano, Koji;Shionoya, Mitsuhiko
预先设计的有机和无机构件的超分子组装已被认为是构建明确的纳米分子的绝佳工具，可在分子器件中得到潜在应用。 [1]特别是，由金属介导的有机配体组装形成的离散中空结构，例如胶囊[2]，由于其内部空间可能发生的化学现象而引起人们极大的兴趣。 [3]然而，用于维持金属组装结构形状的金属数量仍然有限。具有一系列过渡金属离子的金属可交换配位结构将产生大量金属依赖性功能。在这里，我们提出了一种新型盘状三单齿配体 1，它通过自组装方案与一系列二价 d5–d10 过渡金属离子 M2+（M= Mn、Fe、Co、Ni、Pd、Pt、Cu、Zn、Cd 和 Hg）形成 10 个结构等效的配位胶囊 [M6 (1) 8] 12+。所得配合物具有八面体形状的结构，其中六个金属离子位于顶点，八个侧面被八个配体占据1。[Hg6 (1) 8-(CF3SO3) 12]单晶的X射线结构分析揭示了一个3纳米大小的八面体形状的胶囊结构，边长为1.8纳米。其中一些配合物在每个六配位金属中心处具有两个轴向配体，腔内部和外部各一个。请注意，由于从胶囊内部协调的六个 CF3SO3 配体的位点选择性替换，胶囊的内部空间成功地用其他阴离子配体装饰。
Supramolecular assembly of predesigned organic and inorganic building blocks has been recognized as an excellent tool in constructing well-defined nanosized molecules for potential application in molecular devices.[1] In particular, discrete hollow structures such as capsules [2] formed by metal-mediated assembly of organic ligands are of great interest because of the chemical phenomena that may occur in their inner space.[3] However, the number of metals used to maintain the shapes of metal-assembled architectures is still limited. Metal-exchangeable coordination architectures with a series of transition-metal ions would give rise to a large number of metal-dependent functions. Here we present a novel disk-shaped tris-monodentate ligand 1 that forms 10 structurally equivalent coordination capsules,[M6 (1) 8] 12+, with a series of divalent d5–d10 transition-metal ions, M2+(M= Mn, Fe, Co, Ni, Pd, Pt, Cu, Zn, Cd, and Hg) through self-assembly protocols. The resulting complexes have an octahedronshaped structure in which the six metal ions lie on the apexes and the eight sides are occupied with eight ligands 1. X-ray structural analysis of a single crystal of [Hg6 (1) 8-(CF3SO3) 12] revealed a 3-nm-sized octahedron-shaped capsule structure, with sides of 1.8 nm in length. Some of these complexes have two axial ligands at each hexacoordinate metal center, one each from inside and outside the cavity. Note that the inner space of the capsule was successfully decorated with other anionic ligands as a result of the siteselective replacement of the six CF3SO3 À ligands coordinated from inside the capsule.