Modulated preparation and structural diversification of ZnII and CdII metal-organic frameworks with a versatile building block 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol.
Modulated preparation and structural diversification of ZnII and CdII metal-organic frameworks with a versatile building block 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol.
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DOI：
10.1021/ic060129v
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发表时间：
2006-06
影响因子：
4.6
通讯作者：
M. Du;Zhihui Zhang;Xiao‐Jun Zhao;Qiang Xu
中科院分区：
文献类型：
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作者：
M. Du;Zhihui Zhang;Xiao‐Jun Zhao;Qiang Xu
以5-（4-吡啶基）-1，3，4-恶二唑-2-硫醇（Hpyt）为构筑单元，在不同条件下合成了4种新型的Zn（II）和Cd（II）金属有机配位聚合物。通过溶剂热法获得了[Zn 3（pyt）4（OH）2]n（1）和[Cd（pyt）（HCOO）]n（3），而{[Zn（pyt）2（H2O）（2）]。（DMF）2}n（2）和{[Cd（pyt）2]·CHCl 3}n（4）。X射线单晶衍射表明，阴离子配体pyt在1，2和4中采用硫代酰胺异构体，但在3中采用硫醇盐形式。观察到四种类型的结合模式，包括单齿（eta-N（oxa））、双齿（mu-N（py），N（oxa）或mu-N（py），S，S）和三齿（mu-N（py），N（oxa），S）。合成路线和金属配位偏好的差异促进了具有不同网络结构的最终晶体材料的生产，包括具有悬挂臂的1的1D之字形阵列，2的常见2D（4，4）配位层，3的装饰3D α-Po网络，以及前所未有的（3，具有（4（2）.6）2（4（2）.6（2）.8（7）.10（2））拓扑的4的6）-连通3D框架。值得注意的是，DMF溶剂合物的水解导致甲酸根离子的形成，甲酸根离子是3的结构中的组分。配合物2和4显示一维通道，其中的溶剂化物被容纳，即使在排除这些客人，多孔主机框架仍然保留。研究了其热稳定性和气体吸附性能。
Four novel Zn(II) and Cd(II) metal-organic coordination polymers with a versatile building block 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol (Hpyt) have been prepared under different conditions. [Zn3(pyt)4(OH)2]n (1) and [Cd(pyt)(HCOO)]n (3) were obtained through a solvothermal method, whereas {[Zn(pyt)2(H2O)(2)].(DMF)2}n (2) and {[Cd(pyt)2].CHCl3}n (4) were isolated under general conditions. X-ray single-crystal diffraction indicates that the anionic ligand pyt adopts a thioamide isomer in 1, 2, and 4, but a thiolate form in 3. Four types of binding modes involving monodentate (eta-N(oxa)), bidentate (mu-N(py),N(oxa), or mu-N(py),S,S) and tridentate (mu-N(py),N(oxa),S) are observed. The discrepancy of the synthetic routes and metal-coordination preferences facilitates the production of the final crystalline materials with distinct network structures, including a 1D zigzag array of 1 with dangling arms, a common 2D (4,4) coordination layer of 2, a decorated 3D alpha-Po network of 3, and an unprecedented (3,6)-connected 3D framework of 4 with a (4(2).6)2(4(2).6(2).8(7).10(2)) topology. Notably, the hydrolysis of DMF solvates leads to the formation of formate ions, being a component in the structure of 3. Complexes 2 and 4 show 1D channels in which the solvates are accommodated, and even after the exclusion of these guests, the porous host frameworks are still retained. Thermal stability and gas adsorption properties have also been studied.