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Identification of a new electron-transfer relaxation pathway in photoexcited pyrrole dimers

Neville, SP; Kirkby, OM; Kaltsoyannis, N; Worth, GA; Fielding, HH; (2016) Identification of a new electron-transfer relaxation pathway in photoexcited pyrrole dimers. Nature Communications , 7 , Article 11357. 10.1038/ncomms11357. Green open access

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Abstract

Photoinduced electron transfer is central to many biological processes and technological applications, such as the harvesting of solar energy and molecular electronics. The electron donor and acceptor units involved in electron transfer are often held in place by covalent bonds, π–π interactions or hydrogen bonds. Here, using time-resolved photoelectron spectroscopy and ab initio calculations, we reveal the existence of a new, low-energy, photoinduced electron-transfer mechanism in molecules held together by an NH⋯π bond. Specifically, we capture the electron-transfer process in a pyrrole dimer, from the excited π-system of the donor pyrrole to a Rydberg orbital localized on the N-atom of the acceptor pyrrole, mediated by an N–H stretch on the acceptor molecule. The resulting charge-transfer state is surprisingly long lived and leads to efficient electronic relaxation. We propose that this relaxation pathway plays an important role in biological and technological systems containing the pyrrole building block.

Type: Article
Title: Identification of a new electron-transfer relaxation pathway in photoexcited pyrrole dimers
Open access status: An open access version is available from UCL Discovery
DOI: 10.1038/ncomms11357
Publisher version: http://dx.doi.org/10.1038/ncomms11357
Additional information: This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/1496851
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