Departamento de Química Orgánica, Facultad de Química, Campus de Espinardo, Universidad de Murcia, E-30100 Murcia, Spain.
Inorg Chem. 2011 Sep 5;50(17):8214-24. doi: 10.1021/ic200745q. Epub 2011 Aug 10.
The synthesis and electrochemical, optical, and cation-sensing properties of the ferrocene-triazole-pyridine triads 3 and 5 are presented. Azidoferrocene 1 and 1,1'-diazidoferrocene 4 underwent the "click" reaction with 2-ethynylpyridine to give the triads 3 and 5 in 81% and 68% yield, respectively. Electrochemical studies carried out in CH(3)CN in the presence of increasing amounts of Zn(2+), Ni(2+), Cd(2+), Hg(2+), and Pb(2+) metal cations, showed that the wave corresponding to the ferrocene/ferrocenium redox couple is anodically shifted by 70-130 mV for triad 3 and 167-214 mV for triad 5. The maximum shift of the ferrocene oxidation wave was found for 5 in the presence of Zn(2+). In addition, the low-energy band of the absorption spectra of 3 and 5 are red-shifted (Δλ = 5-10 nm) upon complexation with these metal cations. The crystal structures of compounds 3 and 5 and the complex 3(2)·Zn have been determined by single-crystal X-ray methods. (1)H NMR studies as well as density functional theory calculations have been carried out to get information about the binding sites that are involved in the complexation process.
呈现了偕二氮戊环-三氮唑-吡啶三联体 3 和 5 的合成及电化学、光学和阳离子传感性能。叠氮基二茂铁 1 和 1,1'-二叠氮基二茂铁 4 分别与 2-乙炔基吡啶发生“点击”反应，以 81%和 68%的产率得到三联体 3 和 5。在 CH(3)CN 中进行的电化学研究，在存在递增量的 Zn(2+)、Ni(2+)、Cd(2+)、Hg(2+)和 Pb(2+)金属阳离子的情况下，表明对应于二茂铁/二茂铁阳离子氧化还原对的波在三联体 3 中正向移动 70-130 mV，在三联体 5 中正向移动 167-214 mV。在存在 Zn(2+)的情况下，5 中发现了二茂铁氧化波的最大移动。此外，3 和 5 的吸收光谱的低能带在与这些金属阳离子络合时发生红移（Δλ=5-10nm）。通过单晶 X 射线方法确定了化合物 3 和 5 以及配合物3(2)·Zn的晶体结构。进行了 1H NMR 研究以及密度泛函理论计算，以获取有关参与络合过程的结合位点的信息。
