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首页> 外文期刊>Chemistry: A European journal >A New Multifunctional Ferrocenyl-Substituted Ferrocenophane Derivative: Optical and Electronic Properties and Selective Recognition of Mg~(2+) Ions
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A New Multifunctional Ferrocenyl-Substituted Ferrocenophane Derivative: Optical and Electronic Properties and Selective Recognition of Mg~(2+) Ions

机译：一种新型的多功能二茂铁基取代的二茂铁金属衍生物：光学和电子性质以及Mg〜（2+）离子的选择性识别

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摘要

The synthesis, characterisation, and X-ray structure of a new strained asymmetric diferrocene derivative (2) is reported. Compound 2 acts as a highly specific electrochemical and optical Mg~(2+) ion sensor, as revealed by spectroscopic and electrochemical techniques. Thus, in the presence of Mg~(2+), a new redox peak appears in the cyclic voltammogram (CV) that is anodically shifted compared to the E_(1/2) of the free receptor (DELTAE_(1/2) = 340 mV). Diferrocene derivative 2 also gives a highly visual response upon addition of Mg~(2+),namely a change of colour from orange to deep purple. In addition, compound 2 does not show any significant sensing activity in the presence of Ca~(2+) or alkaline ions. On protonation, it is converted into the stable diferrocenylcarbenium salt 4, in which two different modes of stabilisation of the alpha-carbocationic centre are clearly demonstrated by a combination of ~1H NMR and ~(57)Fe Mossbauer spectroscopic measurements. Finally, by a partial (chemical or electrochemical) oxidation, compound 2 forms the asymmetric mixed-valence species 2~+, which can be isolated as the solid salt 6 by using CF_3SO_3~- as a counterion. This mixed-valence species shows a fast intramolecular electrontransfer process, as ascertained by several spectroscopic techniques.
机译：报道了新的应变不对称二茂铁衍生物（2）的合成，表征和X射线结构。如光谱和电化学技术所揭示，化合物2充当高度特异性的电化学和光学Mg〜（2+）离子传感器。因此，在存在Mg〜（2+）的情况下，循环伏安图（CV）中会出现一个新的氧化还原峰，该峰与游离受体的E_（1/2）相比发生了阳极移位（DELTAE_（1/2）= 340毫伏）。二茂铁衍生物2在添加Mg〜（2+）时也具有高度的视觉响应，即颜色从橙色变为深紫色。此外，化合物2在Ca〜（2+）或碱性离子的存在下不显示任何显着的传感活性。质子化后，它被转化为稳定的二铁茂铁基碳鎓盐4，其中〜1H NMR和〜（57）Fe Mossbauer光谱测量的结合清楚地证明了α-碳原子化中心的两种不同稳定模式。最后，通过部分（化学或电化学）氧化，化合物2形成不对称混合价态2〜+，可以使用CF_3SO_3〜-作为抗衡离子将其分离为固体盐6。如几种光谱技术所确定的，这种混合价态物质显示出快速的分子内电子转移过程。

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