Interfacial structure of Co porphyrins on Au(111) electrode: Interaction of porphyrin molecules with substrate |
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Authors: | Masashi Nakamura Risa Imai Nagahiro Hoshi Osami Sakata |
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Institution: | 1. Department of Applied Chemistry and Biotechnology, Graduate School of Engineering, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan;2. Synchrotron X-ray Station at SPring-8, National Institute for Materials Science (NIMS), Kouto 1-1-1, Sayo-gun, Hyogo 679-5148, Japan |
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Abstract: | Interfacial structures of cobalt(II) porphine (CoP) and 2,3,7,8,12,13,17,18‐octaethyl‐21H,23-H-porphine]cobalt(II) (CoOEP) have been studied on Au(111) electrode using electrochemical scanning tunneling microscopy (EC-STM), in-situ X-ray diffraction, and density functional theory (DFT) calculations. The adsorption of porphyrins affects the reconstruction of Au(111) surface. The adsorption of CoP causes a lifting of the reconstruction to a complete 1 × 1 structure of Au(111). On CoOEP modified Au(111), the unit cell periodicity of the reconstructed substrate structure expands compared with the √3 × 23 structure of bare Au(111). The same expanded substrate structure was observed on Au(111) modified with OEP without the coordinated Co ion; the coordinated metal ion of the adsorbed porphyrin molecule does not affect the substrate structure. This result indicates that the interaction of conjugated π electrons of porphyrin with the substrate is stronger than that of the coordinated Co ion. In-situ X-ray diffraction and DFT calculation support non-covalent interaction of porphyrins with the Au(111) surface. |
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