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Jorner, Kjell
Feixas Geronès, Ferran Ayub, Rabia Lindh, Roland Solà i Puig, Miquel Ottosson, Henrik |
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2016 | |
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 8Ï€-electron methano[10]annulene (M10A) dicationic ring and 2) a Hückel aromatic with a neutral closed-shell 10Ï€-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 This work has been supported by the Swedish Research Council (project grant 621-2011-4177), Ministerio de EconomÃa y Competitividad (MINECO) of Spain (Project CTQ2014-54306-P) and the Generalitat de Catalunya (project 2014SGR931, Xarxa de ReferÀncia en QuÃmica Teòrica i Computacional, and ICREA Academia 2014 prize for M.S.). F.F. acknowledges financial support of the Beatriu de Pinûs 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 |
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application/pdf | |
0947-6539 (versió paper) 1521-3765 (versió electrònica) |
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http://hdl.handle.net/10256/12371 | |
eng | |
Wiley-VCH Verlag | |
MINECO/PN 2015-2017/CTQ2014-54306-P AGAUR/2014-2016/2014 SGR-931 Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201504924 Articles publicats (D-Q) |
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© Chemistry - A European Journal, 2016, vol. 22, núm. 8, p. 2793-2800 | |
Tots els drets reservats | |
Anulens
Annulenes Aromaticitat (QuÃmica) Aromaticity (Chemistry) Compostos cÃclics Cyclic compounds |
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Analysis of a Compound Class with Triplet States Stabilized by Potentially Baird Aromatic [10] Annulenyl Dicationic Rings | |
info:eu-repo/semantics/article | |
DUGiDocs |