溶剂控制的铜基金属-有机框架物的合成与荧光性能

doi:10.11944/j.issn.1000-0518.2017.09.170180

摘要/Abstract

摘要：

金属-有机框架物在荧光识别领域表现出良好的应用前景,为探究合成更为精确识别的物质,本文利用二羧酸配体(H₂PAIA=5-丙酰胺基间苯二甲酸)和硝酸铜通过溶剂调控合成了两例结构不同的铜基金属-有机框架物(MOFs) {[Cu(PAIA)(H₂O)]·2H₂O}(1)和{[Cu₃(PAIA)₂(DMSO)(Pyridine)_1.5]}(DMSO:二甲基亚砜;Pyridine:吡啶)(2)。尽管由相同的金属离子和有机配体构筑而成,但显示出具有显著溶剂导向特征的不同框架结构:配合物1为三维NbO型拓扑结构,而配合物2为二维sql型拓扑结构。正是由于这些结构上的差异,导致两个配合物的荧光识别性能和疏水性能展现出显著的不同。配合物1能够同时识别Pb²⁺和Ag⁺离子,而配合物2只能识别Pb²⁺,对Ag⁺没有明显的信号响应。配合物1的疏水角85.06°比配合物2的52.71°有显著的增加。

关键词: 溶剂调控, 金属有机框架物, 拓扑分析, 荧光性能, 疏水性能

Abstract:

Metal-organic frameworks have promising potentials of for applications in the areas of fluorescence recognition. To explore more accurate identification of synthetic substancess, we synthesized two copper metal-organic frameworks(MOFs), {[Cu(PAIA)(H₂O)]·2H₂O}(1) and {[Cu₃(PAIA)₂(DMSO)(Pyridine)_1.5]}(2)(H₂PAIA=5-(propionyl-λ2-azanyl)isophthalic acid; DMSO=dimethyl sulphoxide), by the solvothermal reaction in the presence of H₂PAIA under different solvents(H₂O and DMSO/H₂O). Synthetic investigations and structural analyses reveal that both MOFs show distinct frameworks with remarkable solvent-directed feature, although they are assembled from the same starting materials, i.e., Cu(NO₃)₂·3H₂O with H₂PAIA for complexes 1 and 2. The topological structures and fluorescent properties of the two coordination compounds show a significant difference. Complex 1 is a three-dimensional NbO-type topology, while the complex 2 is a two-dimensional sql-type topology. Complex 1 exhibits fluorescent recognition to both Pb²⁺ and Ag⁺ ions, while complex 2 exhibits fluorescent recognition of Pb²⁺ ion. The water contact angle for complex 1 is 85.06°, while the water contact angle for complex 2 is 52.71°.

Key words: solvent control, metal-organic frameworks, topology analysis, fluorescence properties, hydrophobic properties

王雨桐, 范卫东, 肖振宇, 黄招娣, 徐林, 张亮亮, 邢立学, 戴昉纳, 孙道峰. 溶剂控制的铜基金属-有机框架物的合成与荧光性能[J]. 应用化学, 2017, 34(9): 1035-1045.

WANG Yutong, FAN Weidong, XIAO Zhenyu, HUANG Zhaodi, XU Lin, ZHANG Liangliang, XING Lixue, DAI Fangna, SUN Daofeng. Solvent-Dependent Synthesis and Fluorescent Properties of Cu(Ⅱ) Metal-Organic Frameworks[J]. Chinese Journal of Applied Chemistry, 2017, 34(9): 1035-1045.

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