Dual-Emission Lanthanide-MOF Sensors Enabling Ratiometric Fluorescent Detection of 2,4,6-Trinitrotoluene with High Selectivity.

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-09-21 DOI:10.1021/acs.inorgchem.5c03421

Wei Lv,Nan Song,Yu-Dong Shao,Quan-Guo Zhai

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Abstract

Although designing dual-emission probes remains challenging, mixed-ligand metal-organic frameworks (MOFs) offer a promising platform for ratiometric fluorescent sensors. MOFs with multiple components of different metal centers and/or different ligands provide a great chance for the precise synthesis of ratiometric fluorescent sensors. Herein, N,N'-bis(5-isophthalic acid)-naphthalene diimide (NDI) with a large π-conjugate plane was selected to combine with 2,5-dihydroxyterephthalic acid (DHBDC), a typical molecule with an excited-state intramolecular proton transfer process, to form a mixed-ligand system. Their self-assembly with lanthanide metal ions (Ln3+) under solvothermal conditions led to a series of Ln-MOFs, named [Ln(DHBDC)0.5(NDI)0.5·solvents] (SNNU-380(Ln); Ln = Tb, Eu, Er, Dy, Gd, and Nd; solvents = N,N'-dimethylformamide (DMF) and/or N,N'-dimethylpropyleneurea (DMPU)). As expected, SNNU-380(Ln) exhibits controllable dual fluorescence emissions originating from two fluorescent ligands (420 nm emission from NDI and 550 nm emission from DHBDC) mildly regulated by lanthanide metal ions and shows unique fluorescence quenching for selective 2,4,6-trinitrotoluene (TNT) detection through a photoinduced electron transfer (PET) mechanism. Among them, SNNU-380(Eu) exhibits outstanding detection ability with the highest sensitivity (KSV = 6.80 × 103 M-1), the lowest detection limit (0.18 ppm), a rapid response, exceptional selectivity among nitro-aromatic explosives (NAEs), and excellent recyclability, surpassing the performance of most MOF sensors.

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双发射镧系- mof传感器实现了2,4,6-三硝基甲苯的高选择性比例荧光检测。

虽然设计双发射探针仍然具有挑战性，但混合配体金属有机框架（mof）为比例荧光传感器提供了一个有前途的平台。具有不同金属中心和/或不同配体的多种组分的mof为精确合成比例荧光传感器提供了很大的机会。本文选择π共轭面较大的N，N′-双（5-二苯二甲酸）-萘二亚胺（NDI）与具有激发态分子内质子转移过程的典型分子2,5-二羟基对苯二甲酸（DHBDC）结合，形成混合配体体系。它们在溶剂热条件下与镧系金属离子（Ln3+）自组装，得到了一系列的Ln- mof，命名为[Ln(DHBDC)0.5(NDI)0.5·溶剂](SNNU-380(Ln)；Ln = Tb, Eu, Er, Dy, Gd, Nd；溶剂= N，N'-二甲基甲酰胺（DMF）和/或N，N'-二甲基丙烯脲（DMPU）)。正如预期的那样，SNNU-380（Ln）在镧系金属离子的温和调节下表现出可控的双荧光发射（NDI发射420 nm， DHBDC发射550 nm），并通过光诱导电子转移（PET）机制对选择性2,4,6-三硝基甲苯（TNT）检测表现出独特的荧光猝灭。其中，SNNU-380（Eu）的检测能力突出，灵敏度最高（KSV = 6.80 × 103 M-1），检出限最低（0.18 ppm），响应速度快，对硝基芳香炸药（NAEs）的选择性好，可回收性好，超过了大多数MOF传感器的性能。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.