一种含有Cu₆S₆簇和Zn²⁺的杂金属配合物合成及其荧光传感性质

Synthesis and Fluorescence Sensing Properties of a Heterometallic Complex with Cu₆S₆ Clusters and Zn²⁺

摘要

以2-巯基异烟酸(H₂mna)、Cu⁺和Zn²⁺为原料,采用一锅法进行溶剂热合成,制备一种新型的杂金属配合物{[Cu₆Zn₃(mna)₆(en)3H₂O]∙solvent}_n(1),利用单晶X射线衍射、红外光谱和热重分析对其结构和热稳定性进行表征.实验结果表明:化合物1中的Cu⁺与(mna)^2-通过配位键形成2种阴离子型[Cu₆(mna)₆]^6-金属配体,均含有拟六方柱状的Cu₆S₆簇,Cu₆S₆簇与Zn²⁺连接形成三维网络结构;化合物1在固态时有明显的红光发射,最大发射波长为664nm;化合物1对2-硝基甲苯表现出灵敏的荧光猝灭响应,猝灭常数(K_SV)和检测限分别为2.33×10³(mol/L)^-1和1.20×10^-5mol/L;2-硝基甲苯的猝灭效应主要归因于光诱导电子转移.

Abstract

Using 2-mercaptoisonicotinic acid (H₂mna), Cu⁺ and Zn²⁺ as raw materials, a novel heterometallic complex {[Cu₆Zn₃(mna)₆(en)3H₂O]∙solvent}_n(1) was prepared by solvothermal synthesis using a one-pot method. Its structure and thermal stability were characterized by single crystal X-ray diffraction, infrared spectroscopy and thermogravimetric analysis. The experimental results show that the interactions of Cu⁺ and (mna)^2- in compound 1 form two anionic [Cu₆(mna)₆]^6- metal ligands through coordination bonds, both containing pseudo-hexagonal prismatical Cu₆S₆ clusters, and Cu₆S₆ clusters are connected to Zn²⁺ to form a three-dimensional network structure. Compound 1 exhibits distinct red light emission in the solid state with a maximum emission wavelength of 664 nm. Compound 1 shows a sensitive fluorescence quenching response to 2-nitrotoluene, with quenching constant (K_SV) and detection limit of 2.33×10³ (mol/L)^-1 and 1.20×10^-5 mol/L, respectively. The quenching effect of 2-nitrotoluene is primarily due to photoinduced electron transfer.

关键词

Cu₆S₆簇 / 一锅法 / 杂金属配合物 / 荧光传感

Key words

Cu₆S₆ cluster / one-pot method / heterometallic complex / fluorescence sensing

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基金资助

山西省自然科学基金(2021030212304)

山西省煤矿矿井水处理技术创新中心2024年开放基金