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Cyclophane Molecules Exhibiting Thermally Activated Delayed Fluorescence: Linking Donor Units to Influence Molecular Conformation

Hempe, Matthias; Harrison, Alastair K.; Ward, Jonathan S.; Batsanov, Andrei S.; Fox, Mark A.; Dias, Fernando B.; Bryce, Martin R.

Cyclophane Molecules Exhibiting Thermally Activated Delayed Fluorescence: Linking Donor Units to Influence Molecular Conformation Thumbnail


Authors

Matthias Hempe

Alastair K. Harrison

Jonathan S. Ward



Abstract

The synthetic methodology to covalently link donors to form cyclophane-based thermally activated delayed fluorescence (TADF) molecules is presented. These are the first reported examples of TADF cyclophanes with “electronically innocent” bridges between the donor units. Using a phenothiazine-dibenzothiophene-S,S-dioxide donor–acceptor–donor (D–A–D) system, the two phenothiazine (PTZ) donor units were linked by three different strategies: (i) ester condensation, (ii) ether synthesis, and (iii) ring closing metathesis. Detailed X-ray crystallographic, photophysical and computational analyses show that the cyclophane molecular architecture alters the conformational distribution of the PTZ units, while retaining a certain degree of rotational freedom of the intersegmental D–A axes that is crucial for efficient TADF. Despite their different structures, the cyclophanes and their nonbridged precursors have similar photophysical properties since they emit through similar excited states resulting from the presence of the equatorial conformation of their PTZ donor segments. In particular, the axial–axial conformations, known to be detrimental to the TADF process, are suppressed by linking the PTZ units to form a cyclophane. The work establishes a versatile linking strategy that could be used in further functionalization while retaining the excellent photophysical properties of the parent D–A–D system.

Citation

Hempe, M., Harrison, A. K., Ward, J. S., Batsanov, A. S., Fox, M. A., Dias, F. B., & Bryce, M. R. (2021). Cyclophane Molecules Exhibiting Thermally Activated Delayed Fluorescence: Linking Donor Units to Influence Molecular Conformation. Journal of Organic Chemistry, 86(1), 429-445. https://doi.org/10.1021/acs.joc.0c02174

Journal Article Type Article
Online Publication Date Nov 28, 2020
Publication Date 2021-01
Deposit Date Jun 3, 2021
Publicly Available Date Nov 28, 2021
Journal Journal of Organic Chemistry
Print ISSN 0022-3263
Electronic ISSN 1520-6904
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 86
Issue 1
Pages 429-445
DOI https://doi.org/10.1021/acs.joc.0c02174

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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.joc.0c02174.







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