Direct Measurement of Electron Transfer Rates between Iron(II) Phthalocyanine and Gold with Different Interface Structures

Abstract

Electron transfer in a metal/molecule system has been extensively studied using various methods. In particular, the relation between the structure of metal/molecule junctions and the electron transfer property is of great interest in the research field of molecular devices. In this study, we measured electron transfer rates of iron(II) phthalocyanine/gold system with different junctions to study the contribution of the atomistic interfacial structures to the electron transfer characteristics.An Au single-crystal disk with (111) or (100) orientation was modified with self-assembled monolayers of imidazole-terminated alkanethiols with the alkyl chain of ten carbon atoms (ImC10SH). Then, iron(II) phthalocyanine (FePc) complexes were attached on top of the monolayer through the axial ligation of the central Fe ions with the imidazole groups. The Au-S bonding structure was measured using Surface-enhanced Raman spectroscopy (SERS).1) The electron transfer rate between Au and FePc was measured by analyzing the cyclic voltammogram (CV) of redox behavior for FePc in 0.1 M perchloric acid aqueous solution.SERS measurements showed that the Au-S bonding structures were different between Au(111) and Au(100). According to the peak position of nAu-S, the dominant Au-S structure was determined to be three-fold hollow geometry on Au(111) and two-fold bridge geometry on Au(100). Figure shows the scan rate dependence of CVs of FePc/ImC10SH/Au(100) and FePc/ImC10SH/Au(111). With increasing the scan rate, the peak separation between the oxidation and reduction peaks became larger in both cases. However, the magnitude of the separation was larger for Au(111) than for Au(100), suggesting that the electron transfer through the Au-S junction was slower at the hollow site on Au(111) than at the bridge site on Au(100). The electron transfer rate can be calculated from the relation between the peak separation and the scan rate. We will present detailed quantitative analysis of the electron transfer rate for different Au-S bond structures, alkyl chain lengths, etc.1) M. Inagaki, K. Motobayashi, K, Ikeda, J. Phys. Chem. Lett., 8, 4236 (2017)Figure. Scan rate dependence of CVs of FePc/ImC10SH/Au(100) and, FePc/ImC10SH/Au(111) in 0.1 M perchloric acid aqueous solution. Figure 1