Du Miao, Zhao Xiao-Jun, Wang Ying
College of Chemistry and Life Science, Tianjin Normal University, Tianjin 300074, P. R. China.
Dalton Trans. 2004 Jul 21(14):2065-72. doi: 10.1039/B403498H. Epub 2004 Jun 14.
Six novel inorganic-organic coordination supramolecular networks based on a versatile linking unit 4-pyridylthioacetate (pyta) and inorganic Co(II), Cu(II), Ag(I), Zn(II), Mn(II) and Pb(II) salts have been prepared in water medium and structurally characterized by single-crystal X-ray diffraction analysis. Reaction of CoCl(2).6H(2)O with Hpyta afforded a neutral mononuclear complex Co(pyta)(2)(H(2)O)(4), which exhibits a two-dimensional (2-D) layered architecture through intermolecular O-HO interactions. Reaction of CuCl(2.2H(2)O with Hpyta yielded a neutral one-dimensional (1-D) coordination polymer [Cu(pyta)(2)(H(2)O].0.5H(2)O(2) consisting of rectangle molecular square units, which show a three-dimensional (3-D) supramolecular network through S...S and O-H...O weak interactions. However, when AgNO(3), Zn(OAc)(2).2H(2)O or MnCl(2).4H(2)O salts were used in the above self-assembled processes, the neutral 2-D coordination polymers Ag(pyta)(3), [Zn(pyta)(2)].4H(2)O(4) or [Mn(pyta)(2)(H(2)O)](5) with different topologies were obtained, respectively. While substituting the transition metal ions used in 1-5 with Pb(OAc)(2).3H(2)O, a one-dimensional coordination polymer Pb(pyta)(2)(6), which shows a novel 2-fold interpenetrating 2-D supramolecular architecture through weak SS interactions, was isolated. It is interesting to note that the building block pyta anion exhibits different configurations and coordination modes in the solid structures of complexes 1-6. These results indicate that the versatile nature of this flexible ligand, together with the coordination preferences of the metal centers, play a critical role in construction of these novel coordination polymers or supramolecules. The spectral and thermal properties of these new materials have also been investigated.
基于通用连接单元4-吡啶硫代乙酸酯(pyta)与无机钴(II)、铜(II)、银(I)、锌(II)、锰(II)和铅(II)盐,制备了六种新型无机-有机配位超分子网络,在水介质中合成,并通过单晶X射线衍射分析对其结构进行了表征。CoCl₂·6H₂O与Hpyta反应得到中性单核配合物[Co(pyta)₂(H₂O)₄](1),通过分子间O-H…O相互作用呈现二维(2-D)层状结构。CuCl₂·2H₂O与Hpyta反应生成中性一维(1-D)配位聚合物[[Cu(pyta)₂(H₂O)]·0.5H₂O]ₙ(2),由矩形分子方形单元组成,通过S…S和O-H…O弱相互作用形成三维(三维)超分子网络。然而,当在上述自组装过程中使用AgNO₃、Zn(OAc)₂·2H₂O或MnCl₂·4H₂O盐时,分别得到了具有不同拓扑结构的中性二维配位聚合物[Ag(pyta)]ₙ(3)、[[Zn(pyta)₂]·4H₂O]ₙ(4)或[[Mn(pyta)₂(H₂O)]]ₙ(5)。用Pb(OAc)₂·3H₂O替代1-5中使用的过渡金属离子时,分离得到一维配位聚合物[Pb(pyta)₂]ₙ(6),它通过弱S…S相互作用呈现出新颖的2倍互穿二维超分子结构。值得注意的是,构建单元pyta阴离子在配合物1-6的固体结构中表现出不同的构型和配位模式。这些结果表明,这种柔性配体的通用性以及金属中心的配位偏好,在这些新型配位聚合物或超分子的构建中起着关键作用。还研究了这些新材料的光谱和热性质。