Ultrafast Dynamics of a Molecular Switch from Resonance Raman Spectroscopy: Comparing Visible and UV Excitation.

Resonance Raman spectroscopy probes the ultrafast dynamics of a diarylethene (DAE) molecular switch following excitation into the first two optical absorption bands. Mode-specific resonance enhancements for Raman excitation at visible (750-560 nm) and near-UV (420-390 nm) wavelengths compared with the calculated and experimental off-resonance Raman spectrum at 785 nm reveal different Franck-Condon active vibrations for the two electronically excited states. The resonance enhancements at visible wavelengths are consistent with initial motion on the first excited-state that promotes the cycloreversion reaction, whereas the enhancements for excitation at near-UV wavelengths highlight motions involving conjugated backbone and phenyl ring stretching modes that are orthogonal to the reaction coordinate. The results support a mechanism involving rapid internal conversion from the higher-lying state followed by cycloreversion on the first excited state. These observations provide new information about the reactivity of DAE derivatives following excitation in the visible and near-UV.