Organic donor-acceptor thermally activated delayed fluorescence photocatalysts in the photoinduced dehalogenation of aryl halides
Abstract
We report a family of donor-acceptor thermally activated delayed fluorescent (TADF) compounds based on derivatives of DMAC-TRZ, that are strongly photoreducing. Both Eox and thus E*ox could be tuned via substitution of the DMAC donor with a Hammett series of p-substituted phenyl moieties while Ered remained effectively constant. These compounds were assessed in the photoinduced dehalogenation of aryl halides, and analogues bearing electron withdrawing groups were found to produce the highest yields. Substrates of up to Ered = -2.72 V could be dehalogenated at low PC loading (1 mol%) and under air, conditions much milder than previously reported for this reaction. Spectroscopic and chemical studies demonstrate that all PCs, including literature reference PCs, photodegrade, and that it is these photodegradation products that are responsible for the reactivity.
Citation
Bryden , M A , Crovini , E , Comerford , T , Studer , A & Zysman-Colman , E 2024 , ' Organic donor-acceptor thermally activated delayed fluorescence photocatalysts in the photoinduced dehalogenation of aryl halides ' , Angewandte Chemie International Edition , vol. 63 , no. 24 , e202405081 . https://doi.org/10.1002/anie.202405081
Publication
Angewandte Chemie International Edition
Status
Peer reviewed
ISSN
1433-7851Type
Journal article
Description
We are grateful to the University of St Andrews, Syngenta, and the EPSRC Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT) for financial support [Ph.D. studentship to “M.A.B.”; Grant code: EP/L016419/1]. E.Z.-C. acknowledges EPSRC for support (EP/W007517/1). This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska Curie grant agreement No 812872 (TADFlife). We are thankful to the SFC Saltire Emerging Researcher Scheme for funding the placement of M.A.B to the A.S. lab.Collections
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