Coupled Rocking Motion in a Light-Driven Rotary Molecular Motor

Coupled motion is ubiquitous in Nature as it forms the base for the direction, amplification, propagation, and synchronization of movement. Herein, we present experimental proof for the coupling of the rocking motion of a dihydroanthracene stator moiety with the light induced rotational movement of an overcrowded alkene-based molecular motor. The motor was desymmetrized, introducing two different alkyl substituents to the stator part of the molecular scaffold, resulting in the formation of two diastereomers with opposite axial chirality. The structure of the two isomers is determined with nuclear Overhauser effect spectroscopy NMR and single-crystal X-ray analysis. The desymmetrization enables the study of the coupled motion, that is, rotation and oscillation, by 1H NMR, findings that are further supported by density functional theory calculations. A new handle to regulate the rotational speed of the motor through functionalization in the bottom half was also introduced, as the thermal barrier for thermal helix inversion is found to be largely dependent on the alkyl substituents and its orientation toward the upper half of the motor scaffold. In addition to the commonly observed successive photochemical and thermal steps driving the rotation of the motor, we find that the motor undergoes photochemically driven rotation in three of the four steps of the rotation cycle. Hence, this result extends the scope of molecular motors capable of photon-only rotary behavior.