2026-04-14T04:45:35Zhttps://recercat.cat/oai/requestoai:recercat.cat:10256/121932024-06-18T13:50:57Zcom_2072_452955com_2072_2054col_2072_453073
Analysis of a Compound class with Triplet States Stabilized by Potentially Baird-Aromatic [10] Annulenyl Dicationic Rings
Jorner, Kjell
Feixas Geronès, Ferran
Ayub, Rabia
Lindh, Roland
Solà i Puig, Miquel
Ottosson, Henrik
Ministerio de Economía y Competitividad (Espanya)
Generalitat de Catalunya. Agència de Gestió d'Ajuts Universitaris i de Recerca
Aromaticitat (Química)
Aromaticity (Chemistry)
The low-lying triplet state of a recently published compound (TMTQ, Angew. Chem. Int. Ed. 2015, 20, 5888), was analyzed quantum chemically in light of suggestions that it is influenced by Baird-aromaticity. Two mesomeric structures describe this state; a zwitterionic Baird-aromatic structure with a triplet biradical 8pi-electron methano[10]annulene (M10A) dicationic ring, and a Hückel-aromatic with a neutral closed-shell 10pi-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 FLU aromaticity index into alpha and beta 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
This work has been supported by the Swedish Research Council (project grant 621-2011-4177), Ministerio de Economía y Competitividad (MINECO) of Spain (Project CTQ2014-54306-P) and the Generalitat de Catalunya (project 2014SGR931, Xarxa de
Referència en Química Teòrica i Computacional, and ICREA Academia 2014 prize for M.S.). F.F. acknowledges financial support of the Beatriu de Pinós programme from AGAUR for the postdoctoral grants BP_A_00339 and BP_A2_00022. M.S. and F.F. are grateful to the European Union (EU) for FEDER fund number UNGI10-4E-801
2016-02-17
info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
http://hdl.handle.net/10256/12193
http://hdl.handle.net/10256/12193
eng
info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.201504924
info:eu-repo/semantics/altIdentifier/issn/0947-6539
info:eu-repo/semantics/altIdentifier/eissn/1521-3765
info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-P/ES/ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION. NUEVOS DESARROLLOS EN AROMATICIDAD, FUNCIONALES DE LA DENSIDAD Y QUIMICA SUPRAMOLECULAR/
AGAUR/2014-2016/2014 SGR-931
Tots els drets reservats
info:eu-repo/semantics/openAccess
8 p.
application/pdf
Wiley-VCH Verlag
© Chemistry-A European Journal, 2016, vol. 22, núm. 8, p. 2793-2800
Articles publicats (D-Q)
Jorner, Kjell Feixas Geronès, Ferran Ayub, Rabia Lindh, Roland Solà i Puig, Miquel Ottosson, Henrik 2016 Analysis of a Compound with Triplet States Stabilized by Potentially Baird-Aromatic [10] Annulenyl Dicationic Rings Chemistry-A European Journal 22 8 2793 2800