双配体配位的Ni(Ⅱ)、Cu(Ⅱ)金属配合物的结构和性能

摘要/Abstract

摘要： 本文采用水热合成法制备了两个含有咪唑类配体的配位聚合物:{Ni(nip)(p-bix)(H₂O)₂}_n (1)和{Cu(bbi)(dgc)}_n (2) (nip=5-硝基间苯二甲酸;p-bix=1,4-双(咪唑基-1-甲基)苯;bbi=1,1’-(1,4-丁二基)二咪唑;dgc=3,3-二甲基戊二酸)。通过 X 射线单晶衍射、元素分析、PXRD和TGA对配合物进行表征。结果表明,配合物1为具有规则有序孔道结构的一维双链结构,其孔道结构中的—NO₂赋予金属有机框架(MOF)潜在的应用价值。此外,在分子间氢键的作用下,一维链拓展成三维超分子网络结构。而配合物2则是四连接的{6⁵·8}三维拓扑结构,两个配体通过螺旋式盘绕出规则的孔道架构,丰富的分子间氢键使其骨架结构更加稳固。在2~300 K,外加磁场1 000 Oe的条件下,对这两个配合物进行磁学性质研究,在测定的温度范围内对测试的变温磁化率数据进行居里-外斯线性拟合,拟合得到配合物1和2的居里外斯温度分别为1.73 K和6.78 K,证明两种配合物之间均存在弱的铁磁相互作用。

关键词: 金属有机框架, 配位聚合物, 水热合成, 咪唑衍生物, 铁磁性, 孔道结构

Abstract: In this paper, two coordination polymers containing imidazole ligands and dicarboxylic ligands were prepared by hydrothermal synthesis method: {Ni(nip)(p-bix)(H₂O)₂}_n (1) and{Cu(bbi)(dgc)}_n (2) (nip = 5-Nitroisophthalic acid; p-bix=1,4-Bis(imidazolyl-1-methyl)benzene; bbi=1,1’-(1,4-Butanediyl)diimidazole; dgc=3,3-Dimethylglutaric acid). The complexes were characterized by X-ray single crystal diffraction, elemental analysis, PXRD and TGA. The results show that the complex 1 is an one-dimensional double-stranded structure with a regular and ordered pore structure, and the nitro group (—NO₂) of 5-nitroisophthalic acid (nip) in the pore structure endows metal-organic frame (MOF) with potential application value. Futhermore, it is further extended into a 3D supramolecular architecture via strong hydrogen bonding interactions. While complex 2 featured a 3D network with a 4-connecte {6⁵·8} topological structure, and two mixed ligands of imidazole derivative ligand (bbi) and carboxylic acid ligand (H₂dgc) spirally coiled out an regular pore structure. It was rather remarkable that there are also abundant hydrogen bonds in the structure, which consolidate its 3D framework. In addition, the magnetic property of the two complexes was also investigated at 2 K to 300 K with an external magnetic field of 1 000 Oe and magnetic susceptibility datas were rationally fitted with the Curie-Weiss Law in the measured temperature range with θ=1.73 K and 6.78 K, respectively, indicating weak ferromagnetic interactions among metal ions in two complexes.

Key words: metal-organic frame work, coordination polymer, hydrothermal synthesis, imidazole derivative, ferromagnetic interaction, channel structure

中图分类号:

O641.4

代思玉, 刘宇奇, 李杨华, 王新颖, 李玮, 张青青. 双配体配位的Ni(Ⅱ)、Cu(Ⅱ)金属配合物的结构和性能[J]. 人工晶体学报, 2021, 50(12): 2283-2292.

DAI Siyu, LIU Yuqi, LI Yanghua, WANG Xinying, LI Wei, ZHANG Qingqing. Structure and Properties of Ni(Ⅱ) and Cu(Ⅱ) Metal Complexes Coordinated by Two Ligands[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(12): 2283-2292.

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