State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
Inorg Chem. 2012 Mar 5;51(5):3283-8. doi: 10.1021/ic202737h. Epub 2012 Feb 23.
A series of discrete complexes, [Ni(8)(BTC4A)(2)(μ(6)-CO(3))(2)(μ-CH(3)COO)(4)(dma)(4)]·H(2)O (1), [Ni(8)(BTC4A)(2)(μ(6)-CO(3))(2)(μ-Cl)(2)(μ-HCOO)(2)(dma)(4)]·2DMF·2CH(3)CN (2), [Ni(8)(PTC4A)(2) (μ(6)-CO(3))(2)(μ-CH(3)COO)(4)(dma)(4)]·DMF (3), and [Ni(8)(PTC4A)(2)(μ(6)-CO(3))(2)(μ-OH)(μ-HCOO)(3) (dma)(4)] (4) (p-tert-butylthiacalix[4]arene = H(4)BTC4A, p-phenylthiacalix[4]arene = H(4)PTC4A, dma = dimethylamine, and DMF = N,N'-dimethylformamide), have been prepared under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction analyses, powder XRD, and IR spectroscopy. These four complexes are stacked by dumbbell-like building blocks with one chairlike octanuclear-nickel(II) core, which is capped by two thiacalix[4]arene molecules and connected by two in situ generated carbonato anions and different auxiliary anions. This work implied that not only the solvent molecules but also the upper-rim groups of thiacalix[4]arenes have significant effects on the self-assembly of the dumbbell-like building blocks. The magnetic properties of complexes 1-4 were examined, indicating strong antiferromagnetic interactions between the nickel(II) ions in the temperature range of 50-300 K.
一系列离散的配合物，[Ni(8)(BTC4A)(2)(μ(6)-CO(3))(2)(μ-CH(3)COO)(4)(dma)(4)]·H(2)O（1），[Ni(8)(BTC4A)(2)(μ(6)-CO(3))(2)(μ-Cl)(2)(μ-HCOO)(2)(dma)(4)]·2DMF·2CH(3)CN（2），[Ni(8)(PTC4A)(2)(μ(6)-CO(3))(2)(μ-CH(3)COO)(4)(dma)(4)]·DMF（3），和[Ni(8)(PTC4A)(2)(μ(6)-CO(3))(2)(μ-OH)(μ-HCOO)(3)(dma)(4)]（4）（p-叔丁基硫杂杯[4]芳烃=H(4)BTC4A，p-对苯基硫杂杯[4]芳烃=H(4)PTC4A，dma=二甲基甲酰胺，DMF=N,N'-二甲基甲酰胺），在溶剂热条件下制备，并通过单晶 X 射线衍射分析、粉末 XRD 和红外光谱进行结构表征。这四个配合物由哑铃状结构单元堆积而成，每个单元包含一个椅式八核镍（II）核，由两个硫杂杯[4]芳烃分子封端，并通过两个原位生成的碳酸根阴离子和不同的辅助阴离子连接。这项工作表明，不仅溶剂分子，而且硫杂杯[4]芳烃的上位基团对哑铃状结构单元的自组装有显著影响。对配合物 1-4 的磁性进行了研究，表明镍（II）离子在 50-300 K 的温度范围内存在强烈的反铁磁相互作用。
