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

摘要/Abstract

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

中图分类号:

O641

江涛, 梁晓彤, 廖思燕, 刘小慧, 余嘉俊, 邹霖, 邱燕璇. 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[J]. 人工晶体学报, 2024, 53(2): 307-314.

JIANG Tao, LIANG Xiaotong, LIAO Siyan, LIU Xiaohui, YU Jiajun, ZOU Lin, QIU Yanxuan. Synthesis, Structure and Fluorescence Sensing Property of Manganese Metal-Organic Framework Based on 5-Aminonicotinic Acid[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(2): 307-314.

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