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Direct Observation of Distinctive Electronic States of Ferrocene Moieties in Ferrocene-Bridged Trisporphyrin on Au(111) Using Scanning Tunneling Microscopy/Spectroscopy.

The mechanical and electronic properties of ferrocene-bridged trisporphyrin (Fc2P3), which consists of three porphyrin units bridged via a ferrocene (Fc) moiety and adsorbed onto Au(111), were investigated by a pulse injection method using low-temperature scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). STM images revealed that Fc2P3 adsorbed onto Au(111) adopts a linear arrangement with a herringbone reconstruction structure comprising both Fc and porphyrin moieties. Sequential submolecular-resolution STM images and conformational analyses using a simple molecular model revealed that the ferrocene moiety acts as a molecular ball bearing. The electronic states originating from the ferrocene group were clearly observed by bias voltage-dependent STM images, the dI/dV map, and STS. Distinct electronic states are found approximately 1 eV below Ef in the STS spectrum acquired of Fc, whereas these are absent in the porphyrin spectrum.