The development of photocatalytic reactions has provided many novel opportunities to expand the scope of synthetic organic chemistry. In parallel with progress towards uncovering new reactivity, there is consensus that efforts focused on providing detailed mechanistic insight in order to uncover underlying excited-state reactions are essential to maximise formation of desired products. With this in mind, we have investigated the recently reported sensitization-initiated electron transfer (SenI-ET) reaction for the C-H arylation of activated aryl halides. Using a variety of techniques, and in particular nanosecond transient absorption spectroscopy, we are able to distinguish several characteristic signals from the excited-state species involved in the reaction, and subsequent kinetic analysis under various conditions has facilitated a detailed insight into the likely reaction mechanism.
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http://dx.doi.org/10.1002/anie.201916359 | DOI Listing |
Nat Chem
July 2024
Key Laboratory of Natural Medicine and Immuno-Engineering of Henan Province, Henan University, Kaifeng, P. R. China.
Visible-light-driven photoredox catalysis is known to be a powerful tool for organic synthesis. Its occurrence critically depends on the twice exothermic single-electron transfer processes of photosensitizers, which are governed by the redox properties of the species involved. Hence, the inherently narrow range of redox potentials of photosensitizers inevitably constrains their further availability.
View Article and Find Full Text PDFChem Sci
October 2023
Department of Chemistry, University of Basel St. Johanns-Ring 19 4056 Basel Switzerland
Metal-based photosensitizers commonly undergo quantitative intersystem crossing into photoactive triplet excited states. In contrast, organic photosensitizers often feature weak spin-orbit coupling and low intersystem crossing efficiencies, leading to photoactive singlet excited states. By modifying the well-known acridinium dyes, we obtained a new family of organic photocatalysts, the isoacridones, in which both singlet- and triplet-excited states are simultaneously photoactive.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2020
School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, QLD, 4072, Australia.
The development of photocatalytic reactions has provided many novel opportunities to expand the scope of synthetic organic chemistry. In parallel with progress towards uncovering new reactivity, there is consensus that efforts focused on providing detailed mechanistic insight in order to uncover underlying excited-state reactions are essential to maximise formation of desired products. With this in mind, we have investigated the recently reported sensitization-initiated electron transfer (SenI-ET) reaction for the C-H arylation of activated aryl halides.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2017
Universität Regensburg, Fakultät für Chemie und Pharmazie, 93040, Regensburg, Germany.
Photosynthetic organisms exploit antenna chromophores to absorb light and transfer excitation energy to the reaction center where redox reactions occur. In contrast, in visible-light chemical photoredox catalysis, a single species (i.e.
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