Viridium: A Stable Radical and Its π-Dimerization
The discovery of a stable organic radical formed under mild, clean, and efficient light-mediated conditions is reported. The structure of the stable acridinium-based radical photoproduct was unambiguously established by single-crystal X-ray diffraction, mass spectrometry, and in solution by EPR, UV/vis, and NMR spectroscopies. The photochemical mechanism of its formation has been elucidated by photophysical experiments coupled with EPR experiments and theoretical investigations. This unique aromatic radical is featured by amphoteric redox behavior and π-dimerization properties. Its ability to π-dimerize has been demonstrated in water and in the less studied perfluorohexane, two solvents of opposite polarity. By a simple counterion exchange, direct comparison of π-dimer thermodynamics between both antagonist solvents allowed an elucidation of the solvophobic behavior in perfluorocarbon.
Authors
- Jas S. Ward (ORCID: https://orcid.org/0000-0001-9089-9643)
- David Bardelang (ORCID: https://orcid.org/0000-0002-0318-5958)
- Damien Jardel
- Henri‐Pierre Jacquot de Rouville (ORCID: https://orcid.org/0000-0002-9508-6446)
- Kari T. Rissanen (ORCID: https://orcid.org/0000-0002-7282-8419)
- Nolwenn Le Breton (ORCID: https://orcid.org/0000-0002-5638-9444)
- Laurent Ruhlmann (ORCID: https://orcid.org/0000-0003-1154-2422)
- Jean‐Marc Vincent (ORCID: https://orcid.org/0000-0002-3122-9014)
- Valérie Heitz (ORCID: https://orcid.org/0000-0002-5828-9199)
- Sylvie Choua (ORCID: https://orcid.org/0000-0003-1005-3555)
- Jean-Louis Clément
Institutions
- Centre National de la Recherche Scientifique (FR)
- Université de Bordeaux (FR)
- Aix-Marseille Université (FR)
- Institut des Sciences Moléculaires (FR)
- Institut de Chimie Radicalaire (FR)
- Institut de Chimie de Strasbourg (FR)
- Université de Strasbourg (FR)
- University of Jyväskylä (FI)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2024-12-30
- DOI
- https://doi.org/10.1021/jacs.4c13807
- Citations
- 10
- Primary Topic
- Radical Photochemical Reactions
- Type
- article
- Field-Weighted Citation Impact
- 2.50
Funders
- Aix-Marseille Université
- Agence Nationale de la Recherche
- Université de Strasbourg
- Centre National de la Recherche Scientifique
- Jyväskylän Yliopisto
- Université de Bordeaux