Self-Assembly and External Modulation of a Flexible Porphyrin Derivative on Highly Oriented Pyrolytic Graphite

With the aid of scanning tunneling microscopy, we have examined the two-dimensional hydrogen-bonded networks of carboxyl-functionalized porphyrin derivative H₂TCPp molecules at the heptanoic acid/HOPG interface. Moreover, we have successfully modulated the self-assembly structure of H₂TCPp by introducing 1,2-di(4-pyridyl)ethylene molecules into the assembled system. By performing density functional theory calculations, we also revealed the formation mechanisms of the different assemblies and the modulation process. Comparing the self-assembly structures at the liquid/solid interface with those in bulk crystals, we have obtained deep insight into the differences in H₂TCPp assemblies between 2D and 3D networks. Furthermore, this research is expected to deepen our understanding of on-surface phenomena and to provide a feasible process toward 2D assembly regulation.