Analysis of a Compound Class with Triplet States Stabilized by Potentially Baird Aromatic [10]Annulenyl Dicationic Rings

Chemistry : a European Journal
Kjell JornerHenrik Ottosson

Abstract

The low-lying triplet state of a recently published compound (TMTQ) was analyzed quantum chemically in light of suggestions that it is influenced by Baird aromaticity. Two mesomeric structures describe this state: 1) a zwitterionic Baird aromatic structure with a triplet diradical 8π-electron methano[10]annulene (M10A) dicationic ring and 2) a Hückel aromatic with a neutral closed-shell 10π-electron ring. According to charge and spin density distributions, the Hückel aromatic structure dominates the triplet state (the Baird aromatic contributes at most 12 %), and separation of the aromatic fluctuation index (FLU) into α and β electron contributions emphasizes this finding. The small singlet-triplet energy gap is due to Hückel aromaticity of the M10A ring, clarified by comparison to the smaller analogues of TMTQ. Yet, TMTQ and its analogues are Hückel-Baird hybrids allowing for tuning between closed-shell 4n+2 Hückel aromaticity and open-shell 4n Baird aromaticity.

References

Aug 17, 2002·Organic Letters·Paul Von Ragué Schleyer, Frank Pühlhofer
Oct 28, 2004·Journal of the American Chemical Society·Helene MöllerstedtHenrik Ottosson
Jan 11, 2005·The Journal of Chemical Physics·Eduard MatitoMiquel Solà
Jan 18, 2008·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Sebastien VillaumeHenrik Ottosson
Jul 19, 2008·The Journal of Physical Chemistry. a·Peter B Karadakov
Nov 15, 2008·The Journal of Physical Chemistry. a·Peter B Karadakov
Dec 3, 2008·The Journal of Chemical Physics·Marcos MandadoIgnacio Pérez-Juste
Aug 12, 2009·Angewandte Chemie·Hans Jakob Wörner, Frédéric Merkt
Sep 22, 2011·Journal of the American Chemical Society·Xiaozhang ZhuEiichi Nakamura
Nov 5, 2011·Physical Chemistry Chemical Physics : PCCP·Ferran FeixasMiquel Solà
Dec 14, 2011·Journal of Computational Chemistry·Tian Lu, Feiwu Chen
Nov 24, 2012·Nature Chemistry·Henrik Ottosson
Dec 12, 2012·Chemistry : a European Journal·Alessandro Soncini, Patrick W Fowler
Feb 23, 2013·BMJ Case Reports·Peter Ng
Jan 1, 2014·BMJ Case Reports·Suheil Artul
Jan 17, 2015·The Journal of Chemical Physics·David W SmallMartin Head-Gordon
Apr 11, 2015·Chemical Society Reviews·Ferran FeixasMiquel Solà
May 12, 2015·Chemical Society Reviews·Raffaello Papadakis, Henrik Ottosson
Aug 4, 2015·Journal of the American Chemical Society·Tomoyasu ManiJohn R Miller
Nov 13, 2015·Journal of Computational Chemistry·Francesco AquilanteRoland Lindh

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Citations

Jan 28, 2017·Physical Chemistry Chemical Physics : PCCP·Michael Mauksch, Svetlana B Tsogoeva
Oct 7, 2016·Nature Communications·Raffaello PapadakisHenrik Ottosson
Sep 18, 2020·Chemical Communications : Chem Comm·Dandan ChenMiquel Solà
Nov 5, 2019·Nature Communications·Jinseok KimDongho Kim
Feb 13, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Irene Casademont-ReigEduard Matito
May 22, 2020·Journal of the American Chemical Society·Long WangHongbing Fu

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