Theoretical Simulation of Structural Transformation and Chirality Switch in Host–Guest Self-Assembly

With the aim of investigating the guest-induced structural transformation and chirality switch of host–guest self-assembly at the liquid/solid interface, the molecular self-assembly configurations of 5-(benzyloxy)-isophthalic acid derivative (host) and coronene (guest) were studied at the interface of (S)-2-nonanol/highly oriented pyrolytic graphite by modeling and simulation. The molecular models were established based on scanning tunneling microscopy images. Molecular mechanics and molecular dynamics calculations were performed to calculate the adsorption energy, characteristic hydrogen-bonding parameters, surface density, host–guest interaction, and the structural evolution. It is observed that the structure undergoes a guest-induced responsive rearrangement from a honeycomb into a starfish structure, and the chirality is switchable after the addition of the guest. Furthermore, it is found that the underlying mechanisms of structure transformation and chirality switch are attributed to the roles of energy, size matching, and steric hindrance effect. This work can be utilized for the analogous host–guest self-assembly research and rational design of the host–guest system which can switch chirality.