In this thesis, we investigate the kinetics and functionality of Cu-coordinated pyridyl-porphyrin supramolecular self-assembly on a Au(111) surface, using both scanning tunneling microscopy (STM) and kinetic Monte Carlo (KMC) simulation. Although a rich variety of two dimensional (2D) nanostructures has been created through supramolecular self-assembly method, the formation process and the kinetics that involved are not well understood. We start to explore this field with a simple system, Cu-coordinated pyridyl-porphyrin architectures. In the first stage, we adopt classic nucleation theory as well as modified KMC simulation to extract energetic information, such as diffusion barrier of the molecule and binding energy of the coordination, from the STM images of tetra-pyridyl porphyrin (T...[ Read more ]

In this thesis, we investigate the kinetics and functionality of Cu-coordinated pyridyl-porphyrin supramolecular self-assembly on a Au(111) surface, using both scanning tunneling microscopy (STM) and kinetic Monte Carlo (KMC) simulation. Although a rich variety of two dimensional (2D) nanostructures has been created through supramolecular self-assembly method, the formation process and the kinetics that involved are not well understood. We start to explore this field with a simple system, Cu-coordinated pyridyl-porphyrin architectures. In the first stage, we adopt classic nucleation theory as well as modified KMC simulation to extract energetic information, such as diffusion barrier of the molecule and binding energy of the coordination, from the STM images of tetra-pyridyl porphyrin (TPyP) obtained in various conditions. Based on the above study, we extend our research from single TPyP to a series of porphyrin derivatives that differ at number and arrangement of functional end group. The effect of both internal molecular design and external variables on supramolecular self-assembly is studied. Furthermore, the interaction between porphyrin molecules and copper atoms also attracts our attention, which gives birth of the investigation on coordination and metalation bifuncionality of the 2D networks.