Computational Comparison of Chemical and Isotopic Approaches to Control the Photoisomerization Dynamics of Light-Driven Molecular Motors

[Image: see text] Synthetic molecular motors driven by E/Z photoisomerization reactions are able to produce unidirectional rotary motion because of a structural asymmetry that makes one direction of rotation more probable than the other. In most such motors, this asymmetry is realized through the incorporation of a chemically asymmetric carbon atom. Here, we present molecular dynamics simulations based on multiconfigurational quantum chemistry to investigate whether the merits of this approach can be equaled by an alternative approach that instead exploits isotopic chirality. By first considering an N-methylpyrrolidine–cyclopentadiene motor design, it is shown that isotopically chiral variants of this design undergo faster photoisomerizations than a chemically chiral counterpart, while maintaining rotary photoisomerization quantum yields of similarly high magnitude. However, by subsequently considering a pyrrolinium–cyclopentene design, it is also found that the introduction of isotopic chirality does not provide any control of the directionality of the photoinduced rotations within this framework. Taken together, the results highlight both the potential usefulness of isotopic rather than chemical chirality for the design of light-driven molecular motors, and the need for further studies to establish the exact structural circumstances under which this asymmetry is best exploited.