Axially and Helically Chiral Cationic Radical Bicarbazoles: SOMO-HOMO Level Inversion and Chirality Impact on the Sta- bility of Mono-and Diradical Cations

Sitthichok Kasemthaveechok (1) , Laura Abella (2) , Marion Jean (3) , Marie Cordier (1) , Thierry Roisnel (1) , Nicolas Vanthuyne (3) , Thierry Guizouarn (1) , Olivier Cador (1) , Jochen Autschbach (2) , Jeanne Crassous (1) , Ludovic Favereau (4, 1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 Department of Chemistry [Buffalo]
3 ISM2 - Institut des Sciences Moléculaires de Marseille
4 ScanMAT - Synthèse Caractérisation Analyse de la Matière

We report persistent chiral organic mono-and diradical cations based on bicarbazole molecular design with an unprecedented stability dependence on the type of chirality, namely axial versus helical. An unusual chemical stability was observed for sterically unprotected axial bicarbazole radical, in comparison with monocarbazole and helical bicarbazole ones. Such results were experimentally and theoretically investigated, revealing an inversion in energy of the singly occupied molecular orbital (SOMO) and the doubly highest occupied molecular orbital (HOMO) in both axial and helical bicarbazole monoradicals, along with a subtle difference of electronic coupling between the two carbazole units, which is modulated by their relative dihedral angle and related to the type of chirality. Such findings allowed us to explore in-depth the SOMO-HOMO inversion (SHI) in chiral radical molecular systems and provide new insights regarding its impact on the stability of organic radicals. Finally, these specific electronic properties allowed us to prepare a persistent, intrinsically chiral, diradical which notably displayed near infrared electronic circular dichroism responses up to 1100 nm and almost degenerate singlet-triplet ground states with weak antiferromagnetic interactions evaluated by magnetometry experiments.

Domaines: Chimie organique

Sitthichok Kasemthaveechok, Laura Abella, Marion Jean, Marie Cordier, Thierry Roisnel, et al.. Axially and Helically Chiral Cationic Radical Bicarbazoles: SOMO-HOMO Level Inversion and Chirality Impact on the Sta- bility of Mono-and Diradical Cations. Journal of the American Chemical Society, 2020, 142 (48), pp.20409-20418. ⟨10.1021/jacs.0c08948⟩. ⟨hal-03012514⟩