Direct Probing of the Structure and Electron Transfer of Fullerene/Ferrocene Hybrid on Au(111) Electrodes by in Situ Electrochemical STM

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• 作者：Ting Chen ; Dong Wang ; Li-Hua Gan ; Yutaka Matsuo ; Jing-Ying Gu ; Hui-Juan Yan ; Eiichi Nakamura ; Li-Jun Wan
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：February 26, 2014
• 年：2014
• 卷：136
• 期：8
• 页码：3184-3191
• 全文大小：564K
• 年卷期：v.136,no.8(February 26, 2014)
• ISSN：1520-5126

文摘

The electron donor鈥揳cceptor dyads are an emerging class of materials showing important applications in nonlinear optics, dye-sensitized solar cells, and molecular electronics. Investigation of their structure and electron transfer at the molecular level provides insights into the structure鈥損roperty relationship and can benefit the design and preparation of electron donor鈥揳cceptor dyad materials. Herein, the interface adstructure and electron transfer of buckyferrocene Fe(C₆₀Me₅)Cp, a typical electron donor鈥揳cceptor dyad, is directly probed using in situ electrochemical scanning tunneling microscopy (STM) combined with theoretical simulations. It is found that the adsorption geometry and assembled structure of Fe(C₆₀Me₅)Cp is significantly affected by the electrochemical environments. In 0.1 M HClO₄ solution, Fe(C₆₀Me₅)Cp forms well-ordered monolayers and multilayers on Au(111) surfaces with molecular dimer as the building block. In 0.1 M NaClO₄ solution, typical six-fold symmetric close-packed monolayer with vertically adsorbed Fe(C₆₀Me₅)Cp is formed. Upon electrochemical oxidation, the oxidized Fe(C₆₀Me₅)Cp shows higher brightness in an STM image, which facilitates the direct visualization of the interfacial electrochemical electron transfer process. Theoretical simulation indicates that the electrode potential-activated, one-electron transfer from Fe(C₆₀Me₅)Cp to the electrode leads to the change of the delocalization character of the frontier orbital in the molecule, which is responsible for the STM image contrast change. This result is beneficial for understanding the structure and property of single electron donor鈥揳cceptor dyads. It also provides a direct approach to study the electron transfer of electron donor鈥揳cceptor compounds at the molecular level.