两种具有独特结构的六连接金属有机框架：合成、结构、吸附及磁性
Two Six-Connected MOFs with Distinct Architecture: Synthesis, Structure, Adsorption, and Magnetic Properties.
作者信息
Ren Guo-Jian, Han Song-De, Liu Yan-Qing, Hu Tong-Liang, Bu Xian-He
机构信息
College of Chemistry, Nankai University, Tianjin, 300071, P. R. China.
School of Materials Science and Engineering, National Institute for Advanced Materials, Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin, 300350, P. R. China.
出版信息
Chempluschem. 2016 Aug;81(8):775-779. doi: 10.1002/cplu.201600092. Epub 2016 Apr 1.
By assembling Co ions and a combination of 5-(4-pyridyl)tetrazole (4-ptz) and formate ions, two distinct metal-organic frameworks, [Co (4-ptz) (HCOO)(H O) ] and [Co (4-ptz) (dmf) (HCOO) ] (dmf=N,N'-dimethylformamide), were synthesized. They were both characterized by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. Structural analyses revealed that by slightly modulating the coordination environment of the trinuclear cobalt cluster, two complexes were formed featuring unusual six-connected nets reminiscent of a pyrazole-type linear trinuclear cobalt cluster as compared with the classic eight-connected bcu topology. In addition, [Co (4-ptz) (HCOO)(H O) ] interacted strongly with CO , with an adsorption enthalpy of 29.2 kJ mol , and in a selectivity study, the uptake ratios of CO /N (from a 15:85 mixture) and CO /CH (50:50 mixture) were 77.6 and 37.7, respectively. Magnetic studies on both complexes revealed weak antiferromagnetic coupling between the Co ions.
通过组装钴离子、5-(4-吡啶基)四唑(4-ptz)和甲酸根离子的组合，合成了两种不同的金属有机骨架化合物，即[Co(4-ptz)(HCOO)(H₂O)]和[Co(4-ptz)(dmf)(HCOO)]（dmf=N,N'-二甲基甲酰胺）。它们均通过单晶X射线衍射、红外光谱、热重分析和粉末X射线衍射进行了表征。结构分析表明，通过微调三核钴簇的配位环境，形成了两种配合物，与经典的八连接bcu拓扑结构相比，它们具有不寻常的六连接网络，让人联想到吡唑型线性三核钴簇。此外，[Co(4-ptz)(HCOO)(H₂O)]与CO₂强烈相互作用，吸附焓为29.2 kJ·mol⁻¹，在选择性研究中，CO₂/N₂（来自15:85混合物）和CO₂/CH₄（50:50混合物）的吸收比分别为77.6和37.7。对这两种配合物的磁性研究表明，钴离子之间存在弱反铁磁耦合。
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