Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 Bivio per Sestu, I-09042, Monserrato (CA), Italy.
Dipartimento di Chimica "Ugo Schiff", Università degli Studi di Firenze, Via della Lastruccia 3, I-50019 Sesto Fiorentino, Firenze, Italy.
Chempluschem. 2020 Aug;85(8):1789-1799. doi: 10.1002/cplu.202000444.
The synthesis and coordination properties of two fluorescent chemosensors, featuring [9]aneN (1,4,7-triazacyclononane; L1) and [12]aneNS (1-aza-4,7,10-trithiacyclododecane; L2) as receptor units, and a quinoline pendant arm with an amide group as a functional group spacer are described. The optical responses of L1 and L2 in the presence of several metal ions were analysed in MeCN/H O (1 : 4 v/v) solutions. A selective chelation enhancement of fluorescence (CHEF) effect was observed in the presence of Zn in the case of L1, and in the presence of Cd in the case of L2, following the formation of a 1 : 1 and a 1 : 2 metal/ligand complex, respectively, which was also confirmed by potentiometric measurements. H and C NMR measurements in CD CN/CDCl in combination with molecular mechanics calculations show that for both complexes of L1 and L2 with Zn and Cd , respectively, the coordination of the carbonyl group from the pendant arm could be the origin of the observed optical selectivity.
描述了两种荧光化学传感器的合成和配位性质，它们的受体单元分别为[9]aneN（1,4,7-三氮杂环壬烷；L1）和[12]aneNS（1-氮杂-4,7,10-三硫杂环十二烷；L2），以及带有酰胺基的喹啉侧臂作为官能团间隔物。在 MeCN/H2O（1:4 v/v）溶液中分析了 L1 和 L2 存在多种金属离子时的光学响应。在 L1 中存在 Zn 时观察到荧光螯合增强（CHEF）效应，而在 L2 中存在 Cd 时则观察到 CHEF 效应，分别形成了 1:1 和 1:2 的金属/配体络合物，这也通过电位测量得到了证实。在 CD3CN/CDCl3 中进行的 H 和 13C NMR 测量以及分子力学计算表明，对于 L1 和 L2 与 Zn 和 Cd 形成的配合物，分别来自侧臂的羰基的配位可能是观察到的光学选择性的来源。
