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人工晶体学报 ›› 2024, Vol. 53 ›› Issue (2): 307-314.

• 研究论文 • 上一篇    下一篇

基于5-氨基烟酸的锰金属有机框架的合成、结构及荧光传感性质

江涛1, 梁晓彤1, 廖思燕2, 刘小慧1, 余嘉俊1, 邹霖1, 邱燕璇1   

  1. 1.广东第二师范学院化学与材料科学学院,广州 510303;
    2.广州医科大学药学院,广州 511436
  • 收稿日期:2023-09-04 出版日期:2024-02-15 发布日期:2024-02-04
  • 通信作者: 邱燕璇,实验师。E-mail:qiuyanxuan@gdei.edu.cn
  • 作者简介:江 涛(1964—),男,广东省人,副教授。E-mail:jt@gdei.edu.cn
  • 基金资助:
    广东省普通高校青年创新人才项目(2019KQNCX100);广州市科技计划项目(202002030444);广东第二师范学院高等教育教学研究和改革项目(2022jxgg44)

Synthesis, Structure and Fluorescence Sensing Property of Manganese Metal-Organic Framework Based on 5-Aminonicotinic Acid

JIANG Tao1, LIANG Xiaotong1, LIAO Siyan2, LIU Xiaohui1, YU Jiajun1, ZOU Lin1, QIU Yanxuan1   

  1. 1. School of Chemistry and Materials Science, Guangdong University of Education, Guangzhou 510303, China;
    2. School of Pharmaceutical Sciences, Guangzhou Medical University, Guangzhou 511436, China
  • Received:2023-09-04 Online:2024-02-15 Published:2024-02-04

摘要: 室温下,通过溶液法将5-氨基烟酸(5-Hana)与MnCl2反应,成功合成了一例新的三维Mn(II)金属有机框架[Mn2(5-ana)4(H2O)]n(命名为Mn-MOF)。通过X射线单晶衍射、X射线粉末衍射、元素分析、红外光谱、热重分析、紫外-可见光谱和荧光光谱法对配合物的结构和性质进行表征。结构分析表明,配合物属单斜晶系,具有双节点(2,8)-c配位网络结构,其中[Mn2(CO2)2(H2O)]二聚单元作为8-连接节点,5-ana-配体作为2-连接节点。分子范德瓦耳斯表面静电势(ESP)分析表明,5-ana-配体的第一反应位点在羧基氧原子附近,ESP最小值为-143.37 kcal·mol-1,第二和第三反应位点分别位于吡啶环和氨基氮原子附近。Mn-MOF常温下具有良好的热稳定性。荧光光谱测试显示配合物在256 nm光激发下的最大发射波长为402 nm。更重要的是,Mn-MOF可以通过荧光猝灭实现对Fe3+的选择性识别,且猝灭效率达到98.71%,可作为潜在的荧光探针分析水溶液中的Fe3+

关键词: 5-氨基烟酸, Mn(II), 晶体结构, 金属有机框架, 荧光传感器, 铁离子

Abstract: A new three-dimension manganese(II) metal-organic framework [Mn2(5-ana)4(H2O)]n (namely Mn-MOF) has been successfully constructed by the reaction of 5-aminonicotinic acid (5-Hana) and MnCl2 using solution method at room temperature. The structure and properties of Mn-MOF were characterized by X-ray single-crystal diffraction, X-ray powder diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analysis, ultraviolet-visible spectra and luminescent spectra. Structural analysis reveal that the as-synthesized complex crystallized in the monoclinic system and feature a binodal (2,8)-connected coordination network. The [Mn2(CO2)2(H2O)] dimeric unit acts as 8-connected node and 5-ana- ligand acts as 2-connected node. Electrostatic potential (ESP) on molecular van der Waals surface analysis of 5-ana- ligand shows that the first reactive site exists in the surface close to the oxygen atoms of carboxyl group with the ESP global minimum of -143.37 kcal·mol-1. The second and third reactive sites exist in the nitrogen atoms of pyridine ring and amino, respectively. Mn-MOF displays good thermal stability at room temperature. Fluorescence spectroscopy measurement reveals that the complex shows emission maximum at 402 nm upon 256 nm light excitation. More importantly, Mn-MOF exhibits sensing selectivity for Fe3+ by fluorescence quenching with the quenching efficiency up to 98.71%, which makes it as a potential luminescent sensor for analyzing Fe3+ in aqueous solution.

Key words: 5-aminonicotinic acid, Mn(II), crystal structure, metal-organic framework, fluorescent sensor, iron ion

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