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Comprehensive understanding of multiple resonance thermally activated delayed fluorescence through quantum chemistry calculations

Shizu, Katsuyuki Kaji, Hironori 京都大学 DOI:10.1038/s42004-022-00668-6

2022

概要

Molecules that exhibit multiple resonance (MR) type thermally activated delayed fluorescence (TADF) are highly efficient electroluminescent materials with narrow emission spectra. Despite their importance in various applications, the emission mechanism is still controversial. Here, a comprehensive understanding of the mechanism for a representative MR-TADF molecule (5, 9-diphenyl-5, 9-diaza-13b-boranaphtho[3, 2, 1-de]anthracene, DABNA-1) is presented. Using the equation-of-motion coupled-cluster singles and doubles method and Fermi’s golden rule, we quantitatively reproduced all rate constants relevant to the emission mechanism; prompt and delayed fluorescence, internal conversion (IC), intersystem crossing, and reverse intersystem crossing (RISC). In addition, the photoluminescence quantum yield and its prompt and delayed contributions were quantified by calculating the population kinetics of excited states and the transient photoluminescence decay curve. The calculations also revealed that TADF occurred via a stepwise process of 1) thermally activated IC from the electronically excited lowest triplet state T₁ to the second-lowest triplet state T₂, 2) RISC from T₂ to the lowest excited singlet state S₁, and 3) fluorescence from S₁.

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COMMUNICATIONS CHEMISTRY | (2022)5:53 | https://doi.org/10.1038/s42004-022-00668-6 | www.nature.com/commschem

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Acknowledgements

Additional information

Supplementary information The online version contains supplementary material

available at https://doi.org/10.1038/s42004-022-00668-6.

Correspondence and requests for materials should be addressed to Hironori Kaji.

Peer-review information Communications Chemistry thanks Jianzhong Fan and the

other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Peer-reviewer reports are available.

Reprints and permission information is available at http://www.nature.com/reprints

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in

published maps and institutional affiliations.

K.S. performed the theoretical calculations. H.K. planned and supervised the project. All

authors contributed to the writing of this paper and have approved the final version.

Open Access This article is licensed under a Creative Commons

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Competing interests

© The Author(s) 2022

The quantum chemical calculations using the Gaussian 16 and Q-Chem program

packages were performed on the SuperComputer System, Institute for Chemical

Research, Kyoto University. It was also supported by JSPS KAKENHI grant numbers:

19K05629 and JP20H05840 (Grant-in-Aid for Transformative Research Areas, “Dynamic

Exciton”). We thank Edanz (https://jp.edanz.com/ac) for editing a draft of this paper.

Author contributions

The authors have no competing interests.

COMMUNICATIONS CHEMISTRY | (2022)5:53 | https://doi.org/10.1038/s42004-022-00668-6 | www.nature.com/commschem

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