Heterometal–organic frameworks as highly sensitive and highly selective luminescent probes to detect Cu2+, H2PO4− ions and CTC in aqueous solutions

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL Journal of Molecular Structure Pub Date : 2024-11-06 DOI:10.1016/j.molstruc.2024.140591

Feng Su , Peng-Ze Cheng , Ya-Hui Liu , Xin-Yu Liu , Yan Sun , Shu-Xin Li , Shao-Dong Li , Long Sun , Zhi-Jun Wang

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Abstract

The efficient detection of pollutants in aqueous solutions, such as Cu²⁺, H₂PO₄⁻ and CTC, holds significant implications for human health and environmental preservation. Two new heterometallic Zn^II-Eu^III-MOFs {[ZnEu(BITA)₂(H₂O)Cl]·H₂O}_n (Zn^II-Eu^III-1) and {[ZnEu(BITA)_1.5(H₂O)₂Cl₂]·CH₃CN·H₂O}_n (Zn^II-Eu^III-2) were successfully synthesized by using a π-conjugated imidazolyl-carboxylate H₂BITA ligand under solvothermal conditions. Zn^II-Eu^III-1 exhibits a distinctive 3D framework with 1D homochiral right- and left-handed helical chains constructed based on Zn²⁺ ions. Zn^II-Eu^III-2 presents a 3D network with rhombic channels, wherein heterometallic Zn^II-Eu^III ions are interconnected via carboxylate and imidazolyl groups to generate 1D zigzag chains. The Zn^II-Eu^III-MOFs exhibit bright red luminescence emissions in the solid state. Moreover, Zn^II-Eu^III-1 demonstrates exceptional thermal and chemical stability as well as excellent luminescence properties in aqueous solutions. Zn^II-Eu^III-1 can act as a multi-responsive luminescence sensor for the detection of Cu²⁺, H₂PO₄⁻ and CTC in aqueous solutions through luminescence quenching and enhancement with significant red shifts. Notably, the sensing mechanism for H₂PO₄⁻ can be attributed to hydrogen bonding interactions and the formation of exciplexes between H₂PO₄⁻ and Zn^II-Eu^III-1. Furthermore, the sensing mechanism for CTC may be explained by intermolecular interactions, the existence of competition absorption, IFE and the formation of exciplex between CTC and Zn^II-Eu^III-1.

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杂金属有机框架作为高灵敏度和高选择性发光探针，用于检测水溶液中的 Cu2+、H2PO4- 离子和四氯化碳

有效检测水溶液中的污染物（如 Cu2+、H2PO4- 和四氯化碳）对人类健康和环境保护具有重要意义。利用π-共轭咪唑羧酸盐 H2BITA 配体，在溶热条件下成功合成了两种新型异金属 ZnII-EuIII-MOFs {[ZnEu(BITA)2(H2O)Cl]-H2O}n （ZnII-EuIII-1）和 {[ZnEu(BITA)1.5(H2O)2Cl2]-CH3CN-H2O}n （ZnII-EuIII-2）。ZnII-EuIII-1 显示出独特的三维框架，其 1D 同手性右手和左手螺旋链以 Zn2+ 离子为基础构建而成。ZnII-EuIII-2 呈现出一个具有菱形通道的三维网络，其中异金属 ZnII-EuIII 离子通过羧基和咪唑基相互连接，生成一维之字链。ZnII-EuIII-MOFs 在固态下发出明亮的红色荧光。此外，ZnII-EuIII-1 还具有优异的热稳定性和化学稳定性，在水溶液中也具有出色的发光特性。ZnII-EuIII-1 可以作为一种多响应发光传感器，通过显著红移的发光淬灭和增强，检测水溶液中的 Cu2+、H2PO4- 和四氯化碳。值得注意的是，H2PO4- 的感应机制可归因于氢键相互作用以及 H2PO4- 与 ZnII-EuIII-1 之间形成的共轭物。此外，四氯化碳的传感机制可以用分子间的相互作用、竞争吸收的存在、IFE 以及四氯化碳与 ZnII-EuIII-1 之间形成的复合物来解释。

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来源期刊

Journal of Molecular Structure 化学-物理化学

CiteScore

7.10

自引率

15.80%

发文量

2384

审稿时长

45 days

期刊介绍： The Journal of Molecular Structure is dedicated to the publication of full-length articles and review papers, providing important new structural information on all types of chemical species including: • Stable and unstable molecules in all types of environments (vapour, molecular beam, liquid, solution, liquid crystal, solid state, matrix-isolated, surface-absorbed etc.) • Chemical intermediates • Molecules in excited states • Biological molecules • Polymers. The methods used may include any combination of spectroscopic and non-spectroscopic techniques, for example: • Infrared spectroscopy (mid, far, near) • Raman spectroscopy and non-linear Raman methods (CARS, etc.) • Electronic absorption spectroscopy • Optical rotatory dispersion and circular dichroism • Fluorescence and phosphorescence techniques • Electron spectroscopies (PES, XPS), EXAFS, etc. • Microwave spectroscopy • Electron diffraction • NMR and ESR spectroscopies • Mössbauer spectroscopy • X-ray crystallography • Charge Density Analyses • Computational Studies (supplementing experimental methods) We encourage publications combining theoretical and experimental approaches. The structural insights gained by the studies should be correlated with the properties, activity and/ or reactivity of the molecule under investigation and the relevance of this molecule and its implications should be discussed.