Five Disk-Shaped {MII7} (M = Mn, Fe, Co, Cu, Zn) Clusters and One Capsule-Like {CuII6NaI2} Cluster Assembled from the Same Schiff Base Ligand
Five Disk-Shaped {MII7} (M = Mn, Fe, Co, Cu, Zn) Clusters and One Capsule-Like {CuII6NaI2} Cluster Assembled from the Same Schiff Base Ligand
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由相同希夫碱配体组装而成的五个盘状 {MII7}（M = Mn、Fe、Co、Cu、Zn）簇和一个胶囊状 {CuII6NaI2} 簇
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发表时间：
2016
期刊：
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通讯作者：
Wu
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作者：
Haifeng Zhang;Jin Zhang;Rui Liu;Yahong Li;Wei Liu;Wu
在溶剂热条件下合成了六个过渡金属簇合物[Mn7L6](NO3)2·2CH3OH(1)，[Fe7L6](NO3)2·2CH3OH(2)，[Co7L6](NO3)2·2CH3OH(3)，[Cu7L6](NO3)2(4)，[Zn7L6](NO3)2·2CH3OH(5)和[Cu6Na2L6](NO3)2·4CH3OH(6){H2L=2-(2-hydroxy-3-methoxybenzylideneamino)phenol}。用单晶X射线衍射法确定了1-6的结构。配合物1-5具有盘状的{MII7}核，中心的MII离子和外围的6个MII离子由6个µ3-O原子连接。盘边缘的6个MII离子由6个微米2-O原子以成对的方式桥接。配合物2是一个非常罕见的盘状{Fe7}团簇，其中所有的Fe原子都表现为+2氧化态。此外，这是首次使用相同的Schiff碱配体构建了五个等结构的七核簇合物。络合物6的分子中含有一个囊状的{Cu6Na2}核。在这个核心中，两个钠离子位于胶囊的两个顶点上，{Cu6O6}六角棱柱的12个顶点被交替排列的6个CuII离子和6个O原子占据。光致发光研究表明，5在室温下处于固态时有很强的发光。对多晶样品1-4和6进行了变温直流磁化率研究，对多晶样品3也进行了交流磁化率研究。在零场下观察到了较强的异相χ‘信号，表明3是一类单分子磁体。
Six transition-metal clusters of compositions [Mn7L6](NO3)2·2CH3OH (1), [Fe7L6](NO3)2·2CH3OH (2), [Co7L6](NO3)2·2CH3OH (3), [Cu7L6](NO3)2 (4), [Zn7L6](NO3)2·2CH3OH (5), and [Cu6Na2L6](NO3)2·4CH3OH (6) {H2L = 2-(2-hydroxy-3-methoxybenzylideneamino)phenol} have been synthesized under solvothermal conditions. The structures of 1–6 have been established based on single-crystal X-ray diffraction studies. Complexes 1–5 possess disk-shaped {MII7} cores, with the central MII ion and the six peripheral MII ions being linked by six µ3-O atoms. The six MII ions of the rim of the disk are bridged in a pairwise manner by six µ2-O atoms. Complex 2 is a very rare example of a disk-shaped {Fe7} cluster in which all of the Fe atoms exhibit +2 oxidation state. Furthermore, this is the first time that the five isostructural heptanuclear clusters were constructed by using an identical Schiff base ligand. The molecule of complex 6 contains a capsule-like {Cu6Na2} core. In this core, two sodium ions reside on the two vertices of the capsule and the 12 vertices of the {Cu6O6} hexagonal prism are occupied by alternately arrayed six CuII ions and six O atoms. Photoluminescence studies suggest strong emission for 5 in the solid state at room temperature. Variable-temperature dc magnetic susceptibility studies were carried out on polycrystalline samples of 1–4 and 6. The ac susceptibility studies were also performed with 3. Strong out-of-phase, χ′′, signals were observed for 3 at zero field, suggesting that 3 is a class of single molecule magnet (SMM).