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Impact of Methoxy Substituents on Thermally Activated Delayed Fluorescence and Room-Temperature Phosphorescence in All-Organic Donor–Acceptor Systems

Ward, Jonathan S.; Nobuyasu, Roberto S.; Fox, Mark A.; Aguilar, Juan A.; Hall, David; Batsanov, Andrei S.; Ren, Zhongjie; Dias, Fernando B.; Bryce, Martin R.

Impact of Methoxy Substituents on Thermally Activated Delayed Fluorescence and Room-Temperature Phosphorescence in All-Organic Donor–Acceptor Systems Thumbnail


Authors

Jonathan S. Ward

Roberto S. Nobuyasu

Juan A. Aguilar

David Hall

Andrei S. Batsanov

Zhongjie Ren

Martin R. Bryce



Abstract

Thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP) are known to occur in organic D–A–D and D–A systems where the donor group contains the phenothiazine unit and the acceptor is dibenzothiophene-S,S-dioxide. This study reports the synthesis and characterization of one new D–A and four new D–A–D systems with methoxy groups on the phenothiazine to examine their effect on emission properties in the zeonex matrix. X-ray analysis and highly specialized NMR techniques were used to characterize asymmetric methoxy-substituted derivative 3b, which is chiral at N because of an extremely high flipping barrier at the phenothiazine N atom. Based on hybrid-density functional theory computations, the methoxy substituents tune the relative stabilities of the axial conformers with respect to equatorial conformers of the phenothiazine units, depending on their substitution position. This conformational effect significantly influences both TADF and RTP contributions compared to the parent D–A–D system. It is also demonstrated that the equatorial forms of D–A–D and D–A systems in zeonex exhibit TADF. Additionally, the methoxy groups promote luminescence in D–A–D systems where only axial conformers exist. This work reveals further design opportunities for more efficient TADF and RTP molecules.

Citation

Ward, J. S., Nobuyasu, R. S., Fox, M. A., Aguilar, J. A., Hall, D., Batsanov, A. S., …Bryce, M. R. (2019). Impact of Methoxy Substituents on Thermally Activated Delayed Fluorescence and Room-Temperature Phosphorescence in All-Organic Donor–Acceptor Systems. Journal of Organic Chemistry, 84(7), 3801-3816. https://doi.org/10.1021/acs.joc.8b02848

Journal Article Type Article
Acceptance Date Mar 14, 2019
Online Publication Date Mar 26, 2019
Publication Date Apr 5, 2019
Deposit Date Mar 29, 2019
Publicly Available Date Apr 1, 2019
Journal Journal of Organic Chemistry
Print ISSN 0022-3263
Electronic ISSN 1520-6904
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 84
Issue 7
Pages 3801-3816
DOI https://doi.org/10.1021/acs.joc.8b02848

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Publisher Licence URL
http://creativecommons.org/licenses/by/4.0/

Copyright Statement
Advance online version This is an open access article published under a Creative Commons Attribution (CC-BY)
License, which permits unrestricted use, distribution and reproduction in any medium,
provided the author and source are cited.







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