Tale of Three Dithienylethenes: Following the Photocycloreversion with Ultrafast Spectroscopy and Quantum Dynamics...

Photocycloreversion reactions of three diarylethene derivatives whose structures differ only in the placement of two sulfur atoms in the cyclopentene rings are investigated. Despite the minuscule differences between the molecules, both the yields and times of the photoreactions vary considerably. Using UV-vis and infrared femtosecond spectroscopy and quantum chemical dynamics simulations, we elucidate the relationships among the quantum yield, electronic and vibrational relaxation time, and structural properties of the dithienylethene photoswitches. We show that the local aromaticity of the molecule's central ring could be one of the predictors of the quantum yield and the rate of cycloreversion. While from the perspective of electronic dynamics, the cycloreversion is completed within a few picoseconds at most, all three derivatives exhibit much longer (10-25 ps) nuclear rearrangement times that determine the actual times of stable photoproduct formation.