Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan.
Chem Asian J. 2012 Dec;7(12):2864-71. doi: 10.1002/asia.201200578. Epub 2012 Sep 24.
A stilbene-based compound (1) has been prepared and was highly selective for the detection of cyanide anion in aqueous media even in the presence of other anions, such as F(-), Cl(-), Br(-), I(-), ClO(4)(-), H(2)PO(4)(-), HSO(4)(-), NO(3)(-), and CH(3)CO(2)(-). A noticeable change in the color of the solution, along with a prominent fluorescence enhancement, was observed upon the addition of cyanide. The color change was observed upon the nucleophilic addition of the cyanide anion to the electron-deficient cyanoacrylate group of 1. The spectral changes induced by the reaction were analyzed by comparison with two model compounds, such as compound 2 with dimethyl substituents and compound 3 without a cyanoacrylate group. An intramolecular charge-transfer (ICT) mechanism played a key role in the sensing properties, and the mechanism was supported by DFT/TDDFT calculations.
一种基于二苯乙烯的化合物(1)已被制备出来,它在水相介质中对氰离子具有高度选择性,即使存在其他阴离子,如 F(-)、Cl(-)、Br(-)、I(-)、ClO4(-)、H2PO4(-)、HSO4(-)、NO3(-) 和 CH3CO2(-) 也是如此。在加入氰化物后,溶液的颜色会发生明显变化,同时荧光强度显著增强。这种颜色变化是由于氰化物阴离子对 1 中缺电子的氰基丙烯酸酯基团的亲核加成引起的。通过与两个模型化合物(如具有二甲取代基的化合物 2 和没有氰基丙烯酸酯基团的化合物 3)的比较,分析了反应引起的光谱变化。分子内电荷转移(ICT)机制在传感性能中起着关键作用,该机制得到了 DFT/TDDFT 计算的支持。