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Suppression of Structural Change upon S1–T1 Conversion Assists the Thermally Activated Delayed Fluorescence Process in Carbazole-Benzonitrile Derivatives

  • Masaki Saigo
    Masaki Saigo
    Department of Chemistry, Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395, Japan
    More by Masaki Saigo
  • Kiyoshi Miyata*
    Kiyoshi Miyata
    Department of Chemistry, Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395, Japan
    *E-mail: [email protected]. Phone: +81-92-802-4164.
  • Sei’ichi Tanaka
    Sei’ichi Tanaka
    Department of Chemistry, Tokyo Institute of Technology, O-okayama 2-12-1, H-61, Meguro-ku, Tokyo 152-8550, Japan
  • Hajime Nakanotani
    Hajime Nakanotani
    Center for Organic Photonics and Electronics Research (OPERA), Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395, Japan
    JST, ERATO, Adachi Molecular Exciton Engineering Project, Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395, Japan
  • Chihaya Adachi
    Chihaya Adachi
    Center for Organic Photonics and Electronics Research (OPERA), Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395, Japan
    JST, ERATO, Adachi Molecular Exciton Engineering Project, Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395, Japan
  • , and 
  • Ken Onda*
    Ken Onda
    Department of Chemistry, Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395, Japan
    *E-mail: [email protected]. Phone: +81-92-802-4170.
    More by Ken Onda
Cite this: J. Phys. Chem. Lett. 2019, 10, 10, 2475–2480
Publication Date (Web):April 11, 2019
https://doi.org/10.1021/acs.jpclett.9b00810
Copyright © 2019 American Chemical Society

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    Abstract

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    Thermally activated delayed fluorescence (TADF) molecules are gathering attention for their potential to boost the efficiency of organic light-emitting diodes without precious metals. Minimizing the energy difference between the S1 and T1 states (ΔEST) is a fundamental strategy to accelerate reverse intersystem crossing (RISC). However, the lack of microscopic understanding of the process prevents adequate design strategies for efficient TADF materials. Here, we focused on four carbazole-benzonitrile (Cz-BN) derivatives that possess identical ΔEST but distinct TADF activities. We systematically compared their geometrical dynamics upon photoexcitation using time-resolved infrared (TR-IR) vibrational spectroscopy in conjunction with quantum chemical calculations. We found that the most TADF-active molecule, 4CzBN, shows little structural change after photoexcitation, while the TADF-inactive molecules show relatively large deformation upon S1–T1 conversion. This implies that the suppression of structural deformation is critical for minimizing the activation energy barrier for RISC in cases of the Cz-BN derivatives.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpclett.9b00810.

    • Experimental details, time-resolved PL decay profiles, TR-IR spectra and temporal decay profiles, vibrational mode assignments, simulated spectra, calculated energy results, optimized geometries, and HONTOs and LUNTOs (PDF)

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