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一种基于醚键连接的三羧酸配体的新型(3,6)连接镉配位聚合物:水溶液中的合成、拓扑结构及发光传感性能

A novel (3,6)-connected Cd coordination polymer based on an ether-linked tricarboxylate ligand: synthesis, topology and luminescence sensing properties in aqueous solution.

作者信息

Yu Yu'e, Chen Yuqian, Mi Xiuna, Wang Suna, Lu Jing

机构信息

Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China.

出版信息

Acta Crystallogr C Struct Chem. 2019 Dec 1;75(Pt 12):1666-1674. doi: 10.1107/S2053229619015560. Epub 2019 Nov 26.

Abstract

A novel three-dimensional coordination polymer, namely, poly[[diaquabis(μ-4,4'-bipyridine)bis{μ-5-[(2-carboxyphenoxy)methyl]isophthalato}tricadmium(III)] dimethylformamide monosolvate 2.5-hydrate], {[Cd(CHO)(CHN)(HO)]·2CHNO·5HO}, was obtained by the reaction of ether-linked 5-[(2-carboxyphenoxy)methyl]isophthalic acid (HL) with Cd salts in the presence of 4,4'-bipyridine (bpy) under solvothermal conditions. In this complex, the Cd centres are connected by the carboxylate ligands to form two-dimensional wave-like layers, which are pillared by bpy ligands and extended into a rare three-dimensional (3,6)-connected sqc27 framework. The complex demonstrated good water stability and strong luminescence emissions. It not only possesses excellent luminescence sensing activities toward Fe and CrO in aqueous solution, but can also distinguish between CrO and CrO by luminescence. Furthermore, it could be simply and quickly regenerated at least five times. A study of the sensing mechanism indicated that luminescence quenching may be related to the energy competition between the complex and sensing analytes.

摘要

通过在溶剂热条件下,使醚连接的5-[(2-羧基苯氧基)甲基]间苯二甲酸(HL)与镉盐在4,4'-联吡啶(bpy)存在下反应,得到了一种新型三维配位聚合物,即聚[[二水双(μ-4,4'-联吡啶)双{μ-5-[(2-羧基苯氧基)甲基]间苯二甲酸根}三镉(III)]二甲基甲酰胺单溶剂合物2.5水合物],{[Cd₃(HL)₂(bpy)₂(H₂O)₂]·2CH₃NO·5H₂O}。在该配合物中,镉中心通过羧酸根配体相连形成二维波浪状层,这些层由bpy配体支撑并扩展为罕见的三维(3,6)-连接的sqc₂₇框架。该配合物表现出良好的水稳定性和强发光发射。它不仅对水溶液中的Fe³⁺和Cr₂O₇²⁻具有优异的发光传感活性,还能通过发光区分Cr₂O₇²⁻和CrO₄²⁻。此外,它可以简单快速地再生至少五次。传感机理研究表明,发光猝灭可能与配合物和传感分析物之间的能量竞争有关。

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