Two-Legged Molecular Walker and Curvature: Mechanochemical Ring Migration on Graphene

Attaining controllable molecular motion at the nanoscale can be beneficial for multiple reasons, spanning from optoelectronics to catalysis. Here we study the movement of a two-legged molecular walker by modeling the migration of a phenyl aziridine ring on curved graphene. We find that directional ring migration can be attained on graphene in the cases of both 1D (wrinkled/rippled) and 2D (bubble-shaped) curvature. Using a descriptor approach based on graphene's frontier orbital orientation, we can understand the changes in binding energy of the ring as it translates across different sites with variable curvature and the kinetic barriers associated with ring migration. Additionally, we show that the extent of covalent bonding between graphene and the molecule at different sites directly controls the binding energy gradient, propelling molecular migration. Importantly, one can envision such walkers as carriers of charge and disruptors of local bonding. This study enables a new way to tune the electronic structure of two-dimensional materials for a range of applications.