Structural rearrangement accompanying the ultrafast electrocyclization reaction of a photochromic molecular switch

Probing the structural rearrangement of a model photochromic molecular switch provides a window on the fundamental dynamics of electrocyclization reactions. Taking advantage of resonance-enhanced femtosecond stimulated Raman scattering (FSRS) with a broadly tunable Raman excitation wavelength, we selectively probe the competing dynamics of both the reactive and nonreactive conformers of a diarylethene (DAE) derivative that are simultaneously present in solution. Measurements that preferentially probe the electrocyclization (ring-closing) reaction of the reactive species reveal an unexpectedly slow nuclear rearrangement, stretching to tens of picoseconds, in striking contrast with the prompt electronic dynamics in the formation of the closed-ring isomer. The different results from transient electronic and vibrational spectroscopies reflect the different aspects of the reaction that are probed by each technique, depending on whether one considers the electronic state of the molecule or the structural rearrangement of the nuclei. Using a different Raman excitation wavelength selectively probes the picosecond-scale intersystem crossing dynamics of the nonreactive conformer, revealing the vibrational spectra of the singlet and triplet excited states for the first time. The present study paves the way to a more complete understanding of the structural mechanisms accompanying the reversible photochromic switching process.