Moving beyond cyanoarene thermally activated delayed fluorescence compounds as photocatalysts: an assessment of the performance of a pyrimidyl sulfone photocatalyst in comparison to 4CzIPN

Megan Amy Bryden, Francis David Millward, Tomas Matulaitis, Dongyang Chen, Marco Villa, Andrea Fermi, Sultan Cetin, Paola Ceroni, Eli Zysman-Colman*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

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Abstract

Carbazolyl dicyanobenzene (CDCB) derivates exhibiting thermally activated delayed fluorescence (TADF) have shown themselves to be excellent photocatalysts over recent years, particularly 4CzIPN, although investigation into organic TADF compounds as photocatalysts outside of the CDCB group has been limited. Herein, we report an alternative donor-acceptor TADF structure, 9,9′-(sulfonylbis(pyrimidine-5,2diyl))bis(3,6-di-tert-butyl-9H-carbazole), pDTCz-DPmS, for use as a photocatalyst (PC). A comparison of the electrochemical and photophysical properties of pDTCzDPmS with 4CzIPN in a range of solvents identifies the former as a better ground state reducing agent and photoreductant, while both exhibit similar oxidation capabilities in the ground and excited state. The increased conjugation of pDTCz-DPmS relative to 4CzIPN presents a more intense CT band in the UV-Vis absorption spectrum, aiding in the light absorption of this molecule. Prompt and delayed emission lifetimes are observed for pDTCz-DPmS, confirming the TADF nature, both of which are significantly long lived to participate in productive photochemistry. These combined properties make pDTCz-DPmS useful in photocatalysis reactions, covering a range of photoredox oxidative and reductive quenching reactions, as well as those involving a dual Ni(II) cocatalyst, alongside energy transfer processes. The higher triplet energy and increased photostability of pDTCz-DPmS compared with 4CzIPN were found to be advantages of this organic photocatalyst.
Original languageEnglish
JournalThe Journal of Organic Chemistry
VolumeArticles ASAP
Early online date12 Jul 2022
DOIs
Publication statusE-pub ahead of print - 12 Jul 2022

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