Quantum-Classical Simulations Reveal the Photoisomerization Mechanism of a Prototypical First-Generation Molecular...

Light-driven molecular rotary motors convert the energy of absorbed light into unidirectional rotational motion and are key components in the design of molecular machines. The archetypal class of light-driven rotary motors is chiral overcrowded alkenes, where the rotational movement is achieved through consecutive cis-trans photoisomerization reactions and thermal helix inversion steps. While the thermal steps have been rather well understood by now, our understanding of the photoisomerization reactions of overcrowded alkene-based motors still misses key points that would explain the striking differences in operation efficiency of the known systems. Here, we employ quantum-chemical calculations and nonadiabatic molecular dynamics simulations to investigate the excited-state decay and photoisomerization mechanism in a prototypical alkene-based first-generation rotary motor. We show that the initially excited bright state undergoes an ultrafast relaxation to multiple excited-state minima separated by low energy barriers and reveal a slow picosecond-timescale decay to the ground state, which only occurs from a largely twisted dark excited-state minimum, far from any conical-intersection point. Additionally, we attribute the origin of the high yields of forward photoisomerization in our investigated motor to the favorable topography of the ground-state potential energy surface, which is controlled by the conformation of the central cyclopentene rings.