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

Journal of the American Chemical Society
Sitthichok KasemthaveechokLudovic Favereau

Abstract

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 highest (doubly) 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 w...Continue Reading

References

Mar 28, 1996·Chemical Reviews·Neil G. Connelly, William E. Geiger
Aug 22, 2003·Proceedings of the National Academy of Sciences of the United States of America·Jan H Ardenkjaer-LarsenKlaes Golman
Apr 25, 2006·Physical Chemistry Chemical Physics : PCCP·Florian Weigend
Sep 30, 2008·Journal of the American Chemical Society·Tetsuro KusamotoHiroshi Nishihara
Mar 25, 2010·The Journal of Chemical Physics·Giovanni Scalmani, Michael J Frisch
Feb 16, 2011·Topics in Current Chemistry·Jochen AutschbachMark Rudolph
Mar 17, 2011·Chemical Society Reviews·Tadashi SugawaraKentaro Suzuki
May 18, 2011·Chemical Reviews·Jihane Hankache, Oliver S Wenger
Nov 19, 2011·Angewandte Chemie·Alexander Heckmann, Christoph Lambert
May 23, 2013·Nature Chemistry·Ganna Gryn'ovaMichelle L Coote
Jul 26, 2013·Chemical Reviews·Manabu Abe
Jan 15, 2014·Journal of the American Chemical Society·Paola FranchiMarco Lucarini
Jan 13, 2015·The Journal of Organic Chemistry·Nolan M GallagherAndrzej Rajca
Aug 14, 2015·Angewandte Chemie·Guinevere MathiesRobert G Griffin
Aug 20, 2015·Physical Chemistry Chemical Physics : PCCP·Suranjan ShilDouglas J Klein
Nov 26, 2015·Angewandte Chemie·Prince RavatMichal Juríček
Jan 15, 2016·Chemical Society Reviews·Michel RickhausMichal Juríček
May 25, 2016·Journal of the American Chemical Society·Ying WangAndrzej Rajca
Jan 1, 2015·Wiley Interdisciplinary Reviews. Computational Molecular Science·Ganna Gryn'ovaClemence Corminboeuf
May 4, 2017·Annual Review of Physical Chemistry·Monika Srebro-Hooper, Jochen Autschbach
Oct 11, 2017·Angewandte Chemie·Xiao GuJishan Wu
Dec 15, 2017·The Journal of Physical Chemistry. B·Anil Kumar, Michael D Sevilla
Jan 18, 2018·Angewandte Chemie·Xin AiFeng Li
Feb 10, 2018·Chemical Communications : Chem Comm·Tullimilli Y GopalakrishnaJishan Wu
May 22, 2018·Journal of the American Chemical Society·Yuki InoueShu Seki
Aug 2, 2018·Journal of the American Chemical Society·Prince RavatMichal Juríček
Oct 23, 2018·Journal of the American Chemical Society·Ya-Chu HsiehYao-Ting Wu
Dec 7, 2018·The Journal of Organic Chemistry·Sudesh MallickParthasarathy Venkatakrishnan
Feb 13, 2019·Angewandte Chemie·Kenichi Kato, Atsuhiro Osuka
Mar 1, 2019·Journal of the American Chemical Society·Nolan GallagherAndrzej Rajca
Jul 12, 2019·Chemical Reviews·Kais DhbaibiJeanne Crassous
Jul 18, 2019·Accounts of Chemical Research·Chunchen LiuJishan Wu
Sep 4, 2019·Chemistry : a European Journal·Yoshio Teki
Sep 14, 2019·Angewandte Chemie·Paula Mayorga BurrezoJaume Veciana
Oct 10, 2019·Journal of the American Chemical Society·Chan ShuAndrzej Rajca

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Citations

May 29, 2021·Organic Letters·Ryo MurataManabu Abe
Sep 18, 2021·Organic Letters·Agnieszka BodziochPiotr Kaszyński
Oct 3, 2021·Chemistry : a European Journal·Patthira SumsaleeLudovic Favereau

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