Departamento de Química Orgánica, Facultad de Química, Campus de Espinardo, Universidad de Murcia, E-30100 Murcia, Spain.
J Org Chem. 2010 Jan 1;75(1):162-9. doi: 10.1021/jo9023446.
The synthesis, electrochemical, optical, and anion sensing properties of ferrocene-fused imidazole dyads are presented. Ferrocene-benzobisimidazole dyad 1 behaves as a highly selective redox, chromogenic and fluorescent chemosensor molecule for AcO(-) anion in DMSO/H(2)O: the oxidation redox peak is cathodically shifted (DeltaE(1/2) = -170 mV), perturbation of the UV-vis spectrum, and the emission band is both red-shifted (Delta lambda = 13 nm) and increased (Chelation Enhanced Fluorescence, CHEF = 133) upon complexation with this anion. The related ferrocene-bisbenzimidazole dyad 2 has shown the ability for sensing both H(2)PO(4)(-) and HP(2)O(7)(3-) anions in the same medium. Upon complexation, it also displays a cathodic shift of the redox potential (DeltaE(1/2) = -90 to 80 mV), as well as a clear perturbation of the UV-vis spectrum and an increase in the intensity of the emission band (CHEF = 97-37). However, such magnitudes are smaller than those exhibited by 1. (1)H NMR studies have been carried out to obtain information about the molecular sites which are involved in the binding process.
呈现了二茂铁融合咪唑二联体的合成、电化学、光学和阴离子传感性能。二茂铁-苯并双咪唑二联体 1 表现出对 DMSO/H2O 中 AcO(-)阴离子的高度选择性氧化还原、生色和荧光化学传感器分子的特征：氧化还原峰发生阴极位移（DeltaE(1/2)=-170 mV），紫外可见光谱发生扰动，并且在与该阴离子络合时发射带发生红移（Delta lambda = 13nm）和增强（螯合增强荧光 CHEF = 133）。相关的二茂铁-双苯并咪唑二联体 2 已经显示出在同一介质中同时检测 H2PO4(-)和 HP2O7(3-)阴离子的能力。在络合时，它还显示出氧化还原电位的阴极位移（DeltaE(1/2)=-90 至 80 mV），以及紫外可见光谱的明显扰动和发射带强度的增加（CHEF = 97-37）。然而，这些幅度比 1 所表现出的要小。（1）H NMR 研究已经进行，以获取有关参与结合过程的分子位点的信息。
