Charge-induced isomerization in alkyl imine molecular motors: a reduced energy barrier approach

Abstract

Molecular motors offer promising applications in the fields of nanodevices and biological systems, as the accurate control of directional rotation at the molecular scale holds great potential. In this context, it is highly relevant to study a new class of molecular motors that can undergo isomerization. Since the first report of the chiral N-alkyl imine-based motors, most investigations have focused on the unidirectional rotation process induced by light and heat. However, this work explores an alternative mechanism – the electron-induced stimulating mechanism of the molecular motor. We theoretically investigate how charge injection and extraction can influence molecular rotation. The rotation occurs around the central axle, which is measured as the torsion angle between the rotor and the stator fragments of the molecule against the CN double bond. Our computational study reveals that the introduction of charge reduces the energy barrier, facilitating more favourable molecular rotation than in the neutral singlet state. The charged molecule in a quartet spin state can rotate internally, while that in the doublet state cannot. Our findings provide a molecular scale understanding of the reaction pathways and highlight the significant role of charge in promoting the isomerization and rotational behaviour of the molecular motor.