Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, China.
Dalton Trans. 2013 Mar 14;42(10):3552-60. doi: 10.1039/c2dt32115g. Epub 2013 Jan 2.
A new type of thiacalix[4]arene-based chemosensor 2a and 2b containing amino groups as a binding site and 7-nitrobenzo-2-oxa-1,3-diazole (NBD) as a chromophore have been synthesized and characterized by single crystal X-ray diffraction and by NMR spectroscopic methods. Each receptor acted as a strong colorimetric and fluorometric sensor for silver ions and exhibited significant stepwise deprotonation of NH as evidenced by a bathochromic shift in both the UV-vis absorption and fluorescence emission spectra after addition of an Ag(+) cation. Furthermore, the metal-ligand complex 2a·Ag(+) can be exploited as an ion-pair receptor for the recognition of F(-), AcO(-) or I(-) anions through switching the detection signal output (can been distinguished by 'naked eye'). However, receptor 2b·Ag(+) displays a selective response only to iodide ion. These results could be attributed to the slightly different structural conformation between receptors 2a and 2b, which are derived from a 1,3-alternate-thiacalix[4]arene scaffold, suggesting they play a key role in the selective and binding ability of the host chemosensors.
一种新型的含氨基作为结合位点的硫代杯[4]芳烃基化学传感器 2a 和 2b 和 7-硝基苯并-2-氧杂-1,3-二唑（NBD）作为生色团已经通过单晶 X 射线衍射和 NMR 光谱方法进行了合成和表征。每个受体都充当银离子的强比色和荧光传感器，并表现出明显的逐步去质子化的 NH，这可以通过在加入 Ag(+)阳离子后，在紫外-可见吸收和荧光发射光谱中观察到的红移来证明。此外，金属-配体配合物 2a·Ag(+)可以被用作离子对受体，用于识别 F(-)、AcO(-)或 I(-)阴离子，通过切换检测信号输出（可以通过“肉眼”区分）。然而，受体 2b·Ag(+)仅对碘化物离子显示出选择性响应。这些结果可能归因于受体 2a 和 2b 之间略微不同的结构构象，它们来源于 1,3-交替硫代杯[4]芳烃骨架，表明它们在主体化学传感器的选择性和结合能力中起着关键作用。
