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

doi:10.1002/anie.202002733

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

21 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 language	English
Pages (from-to)	8571-8578
Number of pages	8
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	22
DOIs	https://doi.org/10.1002/anie.202002733
Publication status	Published - 2020 May 25

Bibliographical note

Funding Information:
The research at Yonsei University was mainly supported by the NRF (National Research Foundation of Korea) grant funded by Korea government (NRF‐2016R1E1A1A01943379). This work was also partly supported by AFOSR/AOARD grant (FA2386‐17‐1‐4086). The quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support (KSC‐2019‐CRE‐0201). W.K. acknowledges financial support from the NRF Grant funded by Korean Government (NRF‐2015H1A2A1033685‐Global Ph.D. Fellowship Program).

Funding Information:
The research at Yonsei University was mainly supported by the NRF (National Research Foundation of Korea) grant funded by Korea government (NRF-2016R1E1A1A01943379). This work was also partly supported by AFOSR/AOARD grant (FA2386-17-1-4086). The quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support (KSC-2019-CRE-0201). W.K. acknowledges financial support from the NRF Grant funded by Korean Government (NRF-2015H1A2A1033685-Global Ph.D. Fellowship Program).

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

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)

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10.1002/anie.202002733

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

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.",

author = "Woojae Kim and Taeyeon Kim and Seongsoo Kang and Yongseok Hong and Frank W{\"u}rthner and Dongho Kim",

note = "Funding Information: The research at Yonsei University was mainly supported by the NRF (National Research Foundation of Korea) grant funded by Korea government (NRF‐2016R1E1A1A01943379). This work was also partly supported by AFOSR/AOARD grant (FA2386‐17‐1‐4086). The quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support (KSC‐2019‐CRE‐0201). W.K. acknowledges financial support from the NRF Grant funded by Korean Government (NRF‐2015H1A2A1033685‐Global Ph.D. Fellowship Program). Funding Information: The research at Yonsei University was mainly supported by the NRF (National Research Foundation of Korea) grant funded by Korea government (NRF-2016R1E1A1A01943379). This work was also partly supported by AFOSR/AOARD grant (FA2386-17-1-4086). The quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support (KSC-2019-CRE-0201). W.K. acknowledges financial support from the NRF Grant funded by Korean Government (NRF-2015H1A2A1033685-Global Ph.D. Fellowship Program). Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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month = may,

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Tracking Structural Evolution during Symmetry-Breaking Charge Separation in Quadrupolar Perylene Bisimide with Time-Resolved Impulsive Stimulated Raman Spectroscopy. / Kim, Woojae; Kim, Taeyeon; Kang, Seongsoo et al.

In: Angewandte Chemie - International Edition, Vol. 59, No. 22, 25.05.2020, p. 8571-8578.

Research output: Contribution to journal › Article › peer-review

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AU - Kim, Taeyeon

AU - Kang, Seongsoo

AU - Hong, Yongseok

AU - Würthner, Frank

AU - Kim, Dongho

N1 - Funding Information: The research at Yonsei University was mainly supported by the NRF (National Research Foundation of Korea) grant funded by Korea government (NRF‐2016R1E1A1A01943379). This work was also partly supported by AFOSR/AOARD grant (FA2386‐17‐1‐4086). The quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support (KSC‐2019‐CRE‐0201). W.K. acknowledges financial support from the NRF Grant funded by Korean Government (NRF‐2015H1A2A1033685‐Global Ph.D. Fellowship Program). Funding Information: The research at Yonsei University was mainly supported by the NRF (National Research Foundation of Korea) grant funded by Korea government (NRF-2016R1E1A1A01943379). This work was also partly supported by AFOSR/AOARD grant (FA2386-17-1-4086). The quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with supercomputing resources including technical support (KSC-2019-CRE-0201). W.K. acknowledges financial support from the NRF Grant funded by Korean Government (NRF-2015H1A2A1033685-Global Ph.D. Fellowship Program). Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/5/25

Y1 - 2020/5/25

N2 - 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.

AB - 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.

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

Abstract

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