含萘二磺酸类配体单核Cd(II)配合物传感器对Fe³⁺的高选择性检测

Highly Selective Detection of Fe³⁺ by Mononuclear Cd(II) Complex Sensor Containing Naphthalene Disulfonic Acid Ligands

摘要

在溶剂热条件下, 以四水合硝酸镉为金属源, 1,5-萘二磺酸根(1,5-NDA²⁻)和咪唑(Im)为主、辅配体, 合成了一个具有稳定荧光性质的新型镉配合物Cd(C₃H₄N₂)₄(C₁₀H₆O₆S₂)₂[简写为Cd(Im)₄(1,5-NDA)₂]. 采用X射线单晶衍射和热重分析对其进行了表征. X射线单晶衍射结果表明, 配合物晶体属于单斜晶系的C1c1空间群, 中心离子Cd(II)位于六配位畸变的八面体结构中; 热重分析结果表明, 配合物具有良好的热稳定性. 对Cd(Im)₄(1,5-NDA)₂的荧光性能进行了考察, 固态荧光光谱显示配合物具有较好的荧光性, 其荧光发射主要来自配体的π-π^*跃迁. 采用含时密度泛函理论(TD-DFT)对配合物激发态下的轨道贡献进行了计算. 荧光猝灭实验结果表明, Fe³⁺对配合物的荧光强度具有明显的猝灭作用, 配合物对Fe³⁺的检出限为0.46 μmol/L. 采用多技术联用的方式推测了Fe³⁺对Cd(Im)₄(1,5-NDA)₂可能的荧光猝灭机理. 紫外-可见吸收测试结果表明, Fe³⁺与Cd(Im)₄(1,5-NDA)₂之间发生能量共振转移(FRET); 粉末X射线衍射、红外光谱、电感耦合等离子体质谱、能量色散光谱和X射线光电子能谱表征结果表明, Fe³⁺与Cd(Im)₄(1,5-NDA)₂上的N原子之间存在相互作用. 综上所述, Fe³⁺对Cd(Im)₄(1,5-NDA)₂的荧光猝灭机理为Fe³⁺与配合物之间的FRET及Fe³⁺与配合物上N原子发生相互作用的双路径协同猝灭.

Abstract

A new type of stable fluorescent cadmium complex, Cd(C₃H₄N₂)₄(C₁₀H₆O₆S₂)₂[abbreviated as Cd(Im)₄(1,5-NDA)₂], was synthesized by solvothermal method using cadmium nitrate tetrahydrate as the metal source, 1,5-naphthalenedisulfonate(1,5-NDA²⁻) and iImidazole(Im) as the main and auxiliary ligands. The compound was characterized by X-ray single crystal diffraction and thermogravimetric analysis. The X-ray single crystal diffraction results indicated that the compound belonged to the Monoclinic crystal system with theC1c1 space group, and the central ion Cd(II) was located in the distorted octahedral structure. The thermogravimetric analysis results proved that the compound had good thermal stability. The fluorescence properties of Cd(Im)₄(1,5-NDA)₂ were investigated. The solid-state fluorescence spectra showed that the compound had good fluorescence properties, and its fluorescence emission mainly came from the π-π ^* transition of the ligands. The orbital contributions of the excited state of the complex were calculated using the time-dependent density functional theory(TD-DFT). The fluorescence quenching experiments results indicated that Fe³⁺ had a significant quenching effect on the fluorescence intensity of the complex, and the detection limit of Fe³⁺ recognition by the complex was 0.46 μmol/L. By using the multi-technology combined approach, the possible fluorescence quenching mechanism of Fe³⁺ on Cd(Im)₄(1,5-NDA)₂ was speculated. The results of ultraviolet-visible absorption tests indicated that energy resonance transfer(FRET) occurred between Fe³⁺ and Cd(Im)₄(1,5-NDA)₂. The characterization results of powder X-ray diffraction, infrared spectroscopy, inductively coupled plasma mass spectrometry, energy dispersive spectroscopy and X-ray photoelectron spectroscopy showed that there were interactions between Fe³⁺ and N atoms on Cd(Im)₄(1,5-NDA)₂. In summary, the fluorescence quenching mechanism of Fe³⁺ on Cd(Im)₄(1,5-NDA)₂ is a dual-path cooperative quenching: FRET between Fe³⁺ and the complex and the interactions between Fe³⁺ and the N atoms on the complex.

关键词

镉(II)配合物 / 荧光传感 / Fe³⁺ / 猝灭机理

Key words

Cadmium(II) complex / Fluorescence sensing / Fe³⁺ / Quenching mechanism

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基金资助

教育部产学合作协同育人项目2024年第一批次(230805940290824)