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

Woojae Kim, Taeyeon Kim, Seongsoo Kang, Yongseok Hong, Frank Würthner, Dongho Kim

Research output: Contribution to journalArticlepeer-review

28 Citations (Scopus)

Abstract

Elucidating structural roles in photoinduced charge transfer is indispensable, as nuclear rearrangements are simultaneously usually involved in the dynamics. However, it is hard to evaluate whether the structural changes occur or not by using conventional time-resolved electronic spectroscopy. Here, time-resolved impulsive stimulated Raman spectroscopy is applied to record the evolution of vibrational snapshots during charge-separation dynamics of donor–acceptor–donor-type quadrupolar perylene bisimide in real time. Drastic frequency shifts were observed for several Raman bands with their population kinetics, thus symmetry-breaking charge separation accompanies significant structural changes, as supported by (TD)-DFT calculations. A comparison between time-resolved Raman spectra of the neutral S1 state and the radical anion species shows that the spectral signatures, especially in high-frequency regions, provide important clues to bond length alternation patterns in the PBI core.

Original languageEnglish
Pages (from-to)8571-8578
Number of pages8
JournalAngewandte Chemie - International Edition
Volume59
Issue number22
DOIs
Publication statusPublished - 2020 May 25

Bibliographical note

Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry

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