The influence of nearest-neighbour interactions and assembly dynamics on the transport properties of porphyrin supramolecular assemblies on Au(111)

Here we report on the effect of local molecular organization or “tertiary structure” on the charge transport properties of thiol-tethered tetraphenylporphyrin (ZnTPPF 4 -SC 5 SH) nanoscale clusters of ca. 5 nm in lateral dimension embedded within a dodecanethiol (C12) monolayer on Au(111). The structure of the clusters in the mixed monolayers and their resulting transport properties were monitored by Atomic Force Microscopy (AFM), Scanning Tunneling Microscopy (STM) and Spectroscopy (STS). The mixed films were deposited on Au(111) for a period of one to five days, during which the lateral dimensions of the ZnTPPF 4 -SC 5 SH islands that were formed after one day reduced by nearly 35% on average by five days, accompanied by a noticeable depletion of the surrounding C12 monolayer. These subtle changes in mixed monolayer morphology were accompanied by drastic differences in conductance. The ZnTPPF 4 -SC 5