Modification of the Potential Landscape of Molecular Rotors on Au(111) by the Presence of an STM Tip

Molecular rotors on solid surfaces are fundamental components of molecular machines. No matter whether the rotation is activated by heat, electric field or light, it is determined by the intrinsic rotational potential landscape. Therefore, tuning the potential landscape is of great importance for future applications of controlled molecular rotors. Here, using scanning tunneling microscopy (STM), we demonstrate that both tip-molecule distance and sample bias can modify the rotational potential of molecular rotors. We achieve the potential energy difference variations of ∼0.3 meV/pm and ∼18 meV/V between two configurations of a molecular rotor, a tetra- tert-butyl nickel phthalocyanine molecule on Au(111) substrate. Further analysis indicates that the mechanism of modifying the rotational potential is a combination of the van der Waals interaction and the interaction between the molecular dipole and an electric field. This work provides insight into the methods used to modify the effective rotational potential energy of molecular rotors.