Advanced theoretical design of light-driven molecular rotary motors: enhancing thermal helix inversion and visible-light activation.

In this study, we have advanced the field of light-driven molecular rotary motors (LDMRMs) by achieving two pivotal goals: lowering the thermal helix inversion (THI) barrier and extending the absorption wavelength into the visible spectrum. This study involves the structural reengineering of a second-generation visible LDMRM, resulting in the synthesis of a novel class, specifically, 2-((2 S )-5-methoxy-2-methyl-2,3-dihydro-1 H -cyclopenta[ a ]naphthalen-1-yl)-3-oxo-2,3-dihydro-1 H -dibenzo[ e , g ]indole-6,9-dicarbonitrile. This redesigned motor stands out with its two photoisomerization stages and two thermal helix inversions, featuring exceptionally low THI barriers (4.00 and 2.05 kcal mol -1 at the OM2/MRCI level for the EM → EP and ZM → ZP processes, respectively). Moreover, it displays absorption wavelengths in the visible light range (482.98 and 465.76 nm for the EP and ZP isomers, respectively, at the TD-PBE0-D3/6-31G(d,p) level), surpassing its predecessors in efficiency, as indicated by the narrow HOMO-LUMO energy gap. Ultrafast photoisomerization kinetics (approximately 0.8-1.6 ps) and high quantum yields (around 0.3-0.6) were observed through trajectory surface hopping simulations. Additionally, the simulated time-resolved fluorescence emission spectrum indicates a significantly reduced "dark state" duration (0.09-0.26 ps) in these newly designed LDMRMs compared to the original ones, marking a substantial leap forward in the design and efficiency of LDMRMs.