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基于镉的配位聚合物对铁离子和铬酸根离子的[2 + 2]环加成反应及发光传感

[2 + 2] cycloaddition reaction and luminescent sensing of Fe and CrO ions by a cadmium-based coordination polymer.

作者信息

Zhu Rong-Rong, Wang Tao, Yan Tong, Jia Lei, Xue Zhe, Zhou Jie, Du Lin, Zhao Qi-Hua

机构信息

Key Laboratory of Medicinal Chemistry for Natural Resource Education Ministry, Yunnan University, Kunming 650091, People's Republic of China.

出版信息

Dalton Trans. 2019 Aug 28;48(32):12159-12167. doi: 10.1039/c9dt01696a. Epub 2019 Jul 22.

Abstract

A new cadmium-based coordination polymer (CP), [Cd(bpe)(ceba)(fa)(HO)] (1; fa = formate anions), was constructed by solvothermal reactions of cadmium nitrates with trans-1,2-bis(4'-pyridyl)ethylene ligand (bpe) and 4-(1-carboxy-ethoxy)-benzoic acid (Hceba). The [2 + 2] photodimerization reaction of CP 1 under UV irradiation generated the corresponding photoproduct [Cd(rctt-tpcb)(ceba)(fa)(HO)] (1a; rctt-tpcb = tetrakis(4-pyridyl)-cyclobutane) via a single-crystal-to-single-crystal (SCSC) transformation. Single crystal X-ray diffraction unveiled that CPs 1 and 1a have similar 2D layered structures, except that rctt-tpcb replaced a pair of bpe ligands in the latter. Furthermore, CPs 1 and 1a are good bifunctional luminescent sensors that can detect Fe and CrO ions in a mixed medium of water and DMF and display high sensitivity, selectivity, and anti-jamming capability for the recognition of Fe and CrO ions. Moreover, we also examine in detail the possible luminescent quenching mechanisms of 1 and 1a toward Fe and CrO ions.

摘要

通过硝酸镉与反式-1,2-双(4'-吡啶基)乙烯配体(bpe)和4-(1-羧基乙氧基)苯甲酸(Hceba)的溶剂热反应,构建了一种新型镉基配位聚合物(CP),即[Cd(bpe)(ceba)(fa)(H₂O)] (1;fa = 甲酸根阴离子)。CP 1在紫外光照射下的[2 + 2]光二聚反应通过单晶到单晶(SCSC)转变生成了相应的光产物[Cd(rctt-tpcb)(ceba)(fa)(H₂O)] (1a;rctt-tpcb = 四(4-吡啶基)环丁烷)。单晶X射线衍射表明,CPs 1和1a具有相似的二维层状结构,只是后者中rctt-tpcb取代了一对bpe配体。此外,CPs 1和1a是良好的双功能发光传感器,能够在水和N,N-二甲基甲酰胺(DMF)的混合介质中检测Fe³⁺和Cr₂O₇²⁻离子,并且对Fe³⁺和Cr₂O₇²⁻离子的识别显示出高灵敏度、选择性和抗干扰能力。此外,我们还详细研究了1和1a对Fe³⁺和Cr₂O₇²⁻离子可能的发光猝灭机制。

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