Long‐Lived Charge‐Transfer State in Spiro Compact Electron Donor–Acceptor Dyads Based on Pyromellitimide‐Derived Rhodamine: Charge Transfer Dynamics and Electron Spin Polarization

DOI Web Site Web Site 被引用文献1件
  • Xi Chen
    State Key Laboratory of Fine Chemicals School of Chemical Engineering Dalian University of Technology 2 Ling Gong Road Dalian 116024 P. R. China
  • Andrey A. Sukhanov
    Zavoisky Physical-Technical Institute FRC Kazan Scientific Center of Russian Academy of Sciences Kazan 420029 Russia
  • Yuxin Yan
    State Key Laboratory of Fine Chemicals School of Chemical Engineering Dalian University of Technology 2 Ling Gong Road Dalian 116024 P. R. China
  • Damla Bese
    Department of Engineering Physics Faculty of Engineering Ankara University 06100, Beşevler Ankara Turkey
  • Cagri Bese
    Department of Physics Engineering Hacettepe University 06800 Beytepe Ankara Turkey
  • Jianzhang Zhao
    State Key Laboratory of Fine Chemicals School of Chemical Engineering Dalian University of Technology 2 Ling Gong Road Dalian 116024 P. R. China
  • Violeta K. Voronkova
    Zavoisky Physical-Technical Institute FRC Kazan Scientific Center of Russian Academy of Sciences Kazan 420029 Russia
  • Antonio Barbon
    Dipartimento di Scienze Chimiche Università degli Studi di Padova 35131 Padova Italy
  • Halime Gul Yaglioglu
    Department of Engineering Physics Faculty of Engineering Ankara University 06100, Beşevler Ankara Turkey

書誌事項

公開日
2022-04-21
権利情報
  • http://creativecommons.org/licenses/by/4.0/
DOI
  • 10.1002/anie.202203758
公開者
Wiley

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説明

<jats:title>Abstract</jats:title><jats:p>We observed a long‐lived charge transfer (CT) state in a novel orthogonal compact electron donor–acceptor dyads, with closed form of rhodamine (Rho) as electron donor and pyromellitimide (PI),or thionated PI, as electron acceptor. The two parts in the dyads are connected via a spiro quaternary carbon atom, thus the torsion between the donor and acceptor is completely inhibited, which is beneficial to reduce the reorganization energy and to exploit the Marcus inverted region effect to prolong the CT state lifetime. Femtosecond transient absorption spectra show that the charge separation is rather fast, while nanosecond transient absorption spectra confirmed the formation of long‐lived CT state (2.6 μs). Time‐resolved electron paramagnetic resonance (TREPR) spectra determined the spin multiplicity of the long living state and assigned it to a <jats:sup>3</jats:sup>CT state. Replacement of an oxygen atom in the PI part with a sulfur atom favoring classical intersystem crossing processes, causes a consistently shortening of the lifetime of the <jats:sup>3</jats:sup>CT state (0.29 μs).</jats:p>

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