Controlling the Rotational Barrier of Single Porphyrin Rotors on Surfaces

Artificial molecular machines have played an indispensable role in many chemical and biological processes in recent decades. Among all kinds of molecular machines, molecular rotor systems have attracted increasing attention. In this work, we used density functional theory (DFT) calculations to investigate the rotational behaviors of on-surface molecular rotors based on porphyrin, which is a species of molecule with wide biological and chemical compatibilities. Moreover, our comparative studies demonstrate that macrocycle metalation, supporting substrate replacement, and functional group substitutions can effectively modify the rotational barrier of porphyrin rotors. We believe that these modification methods can further guide the path to achieve highly controllable on-surface molecular rotor systems in future applications.