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Cethrene: The Chameleon of Woodward–Hoffmann Rules


Šolomek, Tomáš; Ravat, Prince; Mou, Zhongyu; Kertesz, Miklos; Juríček, Michal (2018). Cethrene: The Chameleon of Woodward–Hoffmann Rules. Journal of Organic Chemistry, 83(8):4769-4774.

Abstract

We demonstrate that the electrocyclic (EC) ring-closure of cethrene in solution proceeds in a conrotatory mode both thermally and photochemically. The facile photochemical EC process promises that cethrene can serve as an efficient chiroptical switch operated solely by light. As for the thermally activated EC reaction, a low reaction barrier and a solvation effect on the EC rate indicate that the C2-symmetric pathway predicted by DFT calculations might not be the correct mechanism. Instead, we argue that the molecular symmetry decreases along the reaction coordinate as a consequence of the low-energy singlet excited state in this diradicaloid molecule, which might lead to a lower activation energy in accord with that determined through kinetic studies. Cethrene, therefore, represents a thought-provoking molecular chameleon of the Woodward–Hoffmann rules that puts our chemical concepts and intuition to test.

Abstract

We demonstrate that the electrocyclic (EC) ring-closure of cethrene in solution proceeds in a conrotatory mode both thermally and photochemically. The facile photochemical EC process promises that cethrene can serve as an efficient chiroptical switch operated solely by light. As for the thermally activated EC reaction, a low reaction barrier and a solvation effect on the EC rate indicate that the C2-symmetric pathway predicted by DFT calculations might not be the correct mechanism. Instead, we argue that the molecular symmetry decreases along the reaction coordinate as a consequence of the low-energy singlet excited state in this diradicaloid molecule, which might lead to a lower activation energy in accord with that determined through kinetic studies. Cethrene, therefore, represents a thought-provoking molecular chameleon of the Woodward–Hoffmann rules that puts our chemical concepts and intuition to test.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2018
Deposited On:24 Apr 2018 12:21
Last Modified:18 Oct 2019 14:41
Publisher:American Chemical Society (ACS)
ISSN:0022-3263
Additional Information:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.joc.8b00656
OA Status:Green
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1021/acs.joc.8b00656
Project Information:
  • : FunderSNSF
  • : Grant IDPP00P2_170534
  • : Project TitleControl of Spin Interactions in Helical Systems
  • : FunderSNSF
  • : Grant IDPZ00P2_174175
  • : Project TitleThree-Dimensional Molecular Electron Acceptors for Efficient Electron-Transporting Materials
  • : FunderSNSF
  • : Grant IDPZ00P2_148043
  • : Project TitleQuantum Information Processing Devices: Emergence of High-Spin Nanographenes

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