Rapid Electron Transport Phenomenon in the Bis(terpyridine) Metal Complex Wire: Marcus Theory and Electrochemical Impedance Spectroscopy Study

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• 作者：Hiroaki Maeda ; Ryota Sakamoto ; Hiroshi Nishihara
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2015
• 出版时间：October 1, 2015
• 年：2015
• 卷：6
• 期：19
• 页码：3821-3826
• 全文大小：398K
• ISSN：1948-7185

文摘

The authors reported previously that bis(terpyiridne)iron(II) complex oligomer wires possess outstanding long-range intrawire electron transport ability. Here, molecular arrays of gold-electrode鈥揵is(terpyridine)iron(II)鈥揻errocene are constructed by stepwise coordination as simple models of the oligomer wire system. The fast electron transfer between the terminal ferrocene and the gold electrode through the bis(terpyiridne)iron(II) complex unit is studied by potential step chronoamperometry (PSCA) and electrochemical impedance spectroscopy (EIS). Tafel plots derived from PSCA are analyzed based on Marcus theory. The plots reveal greater first-order electron transfer rate constant, weaker electronic coupling between the terminal ferrocene and the gold electrode, and smaller reorganization energy than shown by a conventional ferrocenylalkanethiol self-assembled monolayer. The electron transfer rate constants estimated by EIS agree with the PSCA results.