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基于吡啶基-咪唑-羧基多功能配体的两种新型金属有机框架:选择性CO捕获和多响应发光传感器。

Two novel metal-organic frameworks based on pyridyl-imidazole-carboxyl multifunctional ligand: selective CO capture and multiresponsive luminescence sensor.

作者信息

Feng Dou-Dou, Zhao Yu-Di, Wang Xiao-Qing, Fang Dong-Dong, Tang Jing, Fan Li-Ming, Yang Jie

机构信息

Department of Chemistry, College of Science, North University of China, Taiyuan 030051, China.

Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, and School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252000, China.

出版信息

Dalton Trans. 2019 Aug 7;48(29):10892-10900. doi: 10.1039/c9dt01430f. Epub 2019 May 21.

DOI:10.1039/c9dt01430f
PMID:31111141
Abstract

Two novel metal-organic frameworks, formulated as [Mn(CIP)] (1) and [Ag(CIP)] (2) (HCIP = 4-(4-carboxylphenyl)-2,6-di(4-imidazol-1-yl)phenyl)pyridine), were solvothermally synthesized based on a pyridyl-imidazole-carboxyl multifunctional ligand. The single-crystal X-ray diffraction analysis shows that complex 1 is a 3D microporous framework with uncoordinated imidazole groups, and complex 2 is a 2D + 2D → 2D 3-fold parallel interpenetrated network. Complex 1 exhibited excellent CO selective absorption over N and CH. IAST calculations revealed that the selectivities of 1 for the CO/CH (50 : 50) and CO/N (15 : 85) mixtures were 8.0 and 117 at 273 K under 1 bar, respectively. Moreover, the luminescence investigations displayed that complex 2 is an excellent MOF-based multiresponsive fluorescent probe for Fe, CrO/CrO and the pesticide 2,6-Dich-4-nitroaniline, with high selectivity and sensitivity. Notably, complex 2 exhibited a highly sensitive sensing ability (5.2 × 10 M) and a low detection limit (1.7 × 10 M) for 2,6-Dich-4-nitroaniline. To the best of our knowledge, this is the first Ag-MOF-based fluorescent sensor that can simultaneously detect metal ions, inorganic anions and pesticides.

摘要

基于吡啶基 - 咪唑 - 羧基多功能配体,通过溶剂热法合成了两种新型金属有机框架化合物,化学式分别为[Mn(CIP)] (1) 和[Ag(CIP)] (2)(HCIP = 4-(4 - 羧基苯基)-2,6 - 二(4 - 咪唑 - 1 - 基)苯基吡啶)。单晶X射线衍射分析表明,配合物1是具有未配位咪唑基团的三维微孔框架,配合物2是二维 + 二维→二维的三重平行互穿网络。配合物1对N和CH表现出优异的CO选择性吸收。IAST计算表明,在1 bar、273 K条件下,配合物1对CO/CH(50 : 50)和CO/N(15 : 85)混合物的选择性分别为8.0和117。此外,发光研究表明,配合物2是一种用于检测Fe、CrO/CrO和农药2,6 - 二氯 - 4 - 硝基苯胺的基于金属有机框架的优异多响应荧光探针,具有高选择性和高灵敏度。值得注意的是,配合物2对2,6 - 二氯 - 4 - 硝基苯胺表现出高灵敏度传感能力(5.2×10 M)和低检测限(1.7×10 M)。据我们所知,这是首个能够同时检测金属离子、无机阴离子和农药的基于Ag - MOF的荧光传感器。

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