Tracking Structural Evolution during Symmetry Breaking Charge Separation in Quadrupolar Perylene Bisimide with Time-Resolved Impulsive Stimulated Raman Spectroscopy.

Elucidating structural roles in photoinduced charge transfer is indispensable since nuclear rearrangements are simultaneously involved in the dynamics in most cases. However, it is hard to evaluate whether the structural changes occur or not by using conventional time-resolved electronic spectroscopies. Here, we apply time-resolved impulsive stimulated Raman spectroscopy to record the evolution of vibrational snapshots during charge separation dynamics of donor-acceptor-donor type quadrupolar perylene bisimide (PBI 1 ) in real-time. We observed drastic frequency shifts for a large number of Raman bands with their population kinetics. This signifies that symmetry-breaking charge separation accompanies significant structural changes in 1 , which is clearly supported by (TD)-DFT calculations. Furthermore, a comparison between time-resolved Raman spectra of the neutral S 1 state and the radical anion species demonstrates that the spectral signatures especially in high frequency regions provide important clues to bond length alternation patterns in the PBI core.

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