Sensitization-initiated electron transfer via upconversion: mechanism and photocatalytic applications

Glaser, Felix and Kerzig, Christoph and Wenger, Oliver S.. (2021) Sensitization-initiated electron transfer via upconversion: mechanism and photocatalytic applications. Chemical Science, 12 (29). pp. 9922-9933.

PDF - Accepted Version
Available under License CC BY-NC (Attribution-NonCommercial).


Official URL: https://edoc.unibas.ch/84203/

Downloads: Statistics Overview


Sensitization-initiated electron transfer (SenI-ET) describes a recently discovered photoredox strategy that relies on two consecutive light absorption events, triggering a sequence of energy and electron transfer steps. The cumulative energy input from two visible photons gives access to thermodynamically demanding reactions, which would be unattainable by single excitation with visible light. For this reason, SenI-ET has become a very useful strategy in synthetic photochemistry, but the mechanism has been difficult to clarify due to its complexity. We demonstrate that SenI-ET can operate via sensitized triplet-triplet annihilation upconversion, and we provide the first direct spectroscopic evidence for the catalytically active species. In our system comprised of fac-[Ir(ppy)(3)] as a light absorber, 2,7-di-tert-butylpyrene as an annihilator, and N,N-dimethylaniline as a sacrificial reductant, all photochemical reaction steps proceed with remarkable rates and efficiencies, and this system is furthermore suitable for photocatalytic aryl dehalogenations, pinacol couplings and detosylation reactions. The insights presented here are relevant for the further rational development of photoredox processes based on multi-photon excitation, and they could have important implications in the greater contexts of synthetic photochemistry and solar energy conversion.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Glaser, Felix and Kerzig, Christoph
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
edoc DOI:
Last Modified:09 Aug 2021 09:57
Deposited On:09 Aug 2021 09:57

Repository Staff Only: item control page