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Controlling the S1 Energy Profile by Tuning Excited-State Aromaticity

  • Ryota Kotani
    Ryota Kotani
    Graduate School of Science, Kyoto University, Kitashirakawa Oiwake, Sakyo, Kyoto 606-8502, Japan
    More by Ryota Kotani
  • , 
  • Li Liu
    Li Liu
    Molecular Spectroscopy Laboratory, RIKEN, 2-1 Hirosawa, Wako 351-0198, Japan
    More by Li Liu
  • , 
  • Pardeep Kumar
    Pardeep Kumar
    Molecular Spectroscopy Laboratory, RIKEN, 2-1 Hirosawa, Wako 351-0198, Japan
    Ultrafast Spectroscopy Research Team, RIKEN Center for Advanced Photonics (RAP), 2-1, Hirosawa, Wako 351-0198, Japan
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  • , 
  • Hikaru Kuramochi
    Hikaru Kuramochi
    Molecular Spectroscopy Laboratory, RIKEN, 2-1 Hirosawa, Wako 351-0198, Japan
    Ultrafast Spectroscopy Research Team, RIKEN Center for Advanced Photonics (RAP), 2-1, Hirosawa, Wako 351-0198, Japan
    PRESTO, Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012, Japan
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  • , 
  • Tahei Tahara*
    Tahei Tahara
    Molecular Spectroscopy Laboratory, RIKEN, 2-1 Hirosawa, Wako 351-0198, Japan
    Ultrafast Spectroscopy Research Team, RIKEN Center for Advanced Photonics (RAP), 2-1, Hirosawa, Wako 351-0198, Japan
    *[email protected]
    More by Tahei Tahara
    Orcidhttp://orcid.org/0000-0002-6340-8535
  • , 
  • Pengpeng Liu
    Pengpeng Liu
    Graduate School of Science, Kyoto University, Kitashirakawa Oiwake, Sakyo, Kyoto 606-8502, Japan
    More by Pengpeng Liu
  • , 
  • Atsuhiro Osuka
    Atsuhiro Osuka
    Graduate School of Science, Kyoto University, Kitashirakawa Oiwake, Sakyo, Kyoto 606-8502, Japan
    More by Atsuhiro Osuka
    Orcidhttp://orcid.org/0000-0001-8697-8488
  • , 
  • Peter B. Karadakov*
    Peter B. Karadakov
    Department of Chemistry, University of York, Heslington, York YO10 5DD, U.K.
    *[email protected]
    More by Peter B. Karadakov
  • , and 
  • Shohei Saito*
    Shohei Saito
    Graduate School of Science, Kyoto University, Kitashirakawa Oiwake, Sakyo, Kyoto 606-8502, Japan
    PRESTO, Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012, Japan
    *[email protected]
    More by Shohei Saito
    Orcidhttp://orcid.org/0000-0003-1863-9956
Cite this: J. Am. Chem. Soc. 2020, 142, 35, 14985–14992
Publication Date (Web):August 10, 2020
https://doi.org/10.1021/jacs.0c05611
Copyright © 2020 American Chemical Society
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Abstract

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The shape of the lowest singlet excited-state (S1) energy profile is of primary importance in photochemistry and related materials science areas. Here we demonstrate a new approach for controlling the shape of the S1 energy profile which relies on tuning the level of excited-state aromaticity (ESA). In a series of fluorescent π-expanded oxepins, the energy decrease accompanying the bent-to-planar conformational change in S1 becomes less pronounced with lower ESA levels. Stabilization energies following from ESA were quantitatively estimated to be 10–20 kcal/mol using photophysical data. Very fast planarization dynamics in S1 was revealed by time-resolved fluorescence spectroscopy. The time constants were estimated to be shorter than 1 ps, regardless of molecular size and level of ESA, indicating barrierless S1 planarization within the oxepin series.

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