A highly preorganized chemosensor molecule 1 based on a ferrocenyl-guanidine decorated with a chromogenic aryl azo moiety recognizes the acetate anion in acetonitrile solution. At first, receptor 1 underwent two-step oxidation events. Initially, oxidation of 1 occurs at the Fe(II) centre (Ep = 440 mV) to form a ferrocenium species, followed by fast electron transfer from the guanidine moiety of the receptor to the Fe(III) centre with concomitant generation of an Fe(II) species with a radical cation centred at the nitrogen atom. In the second step, the radical cation species formed should undergo electrochemical oxidation at higher potential (Ep = 830 mV). This assumption is supported by spectroelectrochemical studies. A remarkable cathodic shift (182 mV) of the ferrocene/ferrocenium oxidation peak (Ep = 440 mV) and a progressive red-shift (Δλ = 30 nm) of the low energy band are observed in its absorption spectrum upon complexation of receptor 1 with the acetate anion. This change in the absorption spectrum is accompanied by a colour change from yellow to orange, which can be used for the “naked-eye” detection of this anion. Its monoprotonated form is able to selectively sense the less basic Cl−, Br−, NO3−, and HSO4− anions: the oxidation redox peak at Ep = 865 mV is cathodically shifted (107–182 mV).
高度预组织化的
化学传感器分子 1 以
二茂铁基
胍为基础,装饰有可发色的芳基偶氮分子,可识别
乙腈溶液中的
乙酸阴离子。起初,受体 1 经历了两步氧化过程。首先,1 在
铁(II)中心发生氧化(Ep = 440 mV),形成一种
铁络合物,然后电子从受体的
胍基快速转移到
铁(III)中心,同时产生一种以氮原子为中心带有自由基阳离子的
铁(II)物质。在第二步中,形成的自由基阳离子物种应在较高的电位(Ep = 830 mV)下进行电
化学氧化。这一假设得到了光谱电
化学研究的支持。受体 1 与
醋酸阴离子络合后,
二茂铁/
二茂铁氧化峰(Ep = 440 mV)发生了明显的阴极移动(182 mV),其吸收光谱中的低能带也逐渐发生了红移(Δλ = 30 nm)。吸收光谱的这种变化伴随着从黄色到橙色的颜色变化,可用于 "肉眼 "检测这种阴离子。它的
单质子化形式能够选择性地感应碱性较弱的 Cl-、Br-、
NO3- 和 HSO4-阴离子:Ep = 865 mV 处的氧化还原峰会发生阴极移动(107-182 mV)。