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Analysis of a Compound Class with Triplet States Stabilized by Potentially Baird Aromatic [10]Annulenyl Dicationic Rings
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Fysikalisk-organisk kemi.
Univ Girona, IQCC, Campus Montilivi S-N, Girona 17071, Catalonia, Spain.;Univ Girona, Dept Quim, Campus Montilivi S-N, Girona 17071, Catalonia, Spain..
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - BMC, Fysikalisk-organisk kemi.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - Ångström, Teoretisk kemi. Uppsala Univ, Uppsala Ctr Computat Chem UC3, Box 518, S-75120 Uppsala, Sweden..
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2016 (Engelska)Ingår i: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 22, nr 8, s. 2793-2800Artikel i tidskrift (Refereegranskat) Published
Resurstyp
Text
Abstract [en]

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 8-electron methano[10]annulene (M10A) dicationic ring and 2)a Huckel aromatic with a neutral closed-shell 10-electron ring. According to charge and spin density distributions, the Huckel aromatic structure dominates the triplet state (the Baird aromatic contributes at most 12%), and separation of the aromatic fluctuation index (FLU) into and electron contributions emphasizes this finding. The small singlet-triplet energy gap is due to Huckel aromaticity of the M10A ring, clarified by comparison to the smaller analogues of TMTQ. Yet, TMTQ and its analogues are Huckel-Baird hybrids allowing for tuning between closed-shell 4n+2 Huckel aromaticity and open-shell 4n Baird aromaticity.

Ort, förlag, år, upplaga, sidor
2016. Vol. 22, nr 8, s. 2793-2800
Nyckelord [en]
annulenes, aromaticity, Baird's rule, diradical species, electronic structure
Nationell ämneskategori
Kemi
Identifikatorer
URN: urn:nbn:se:uu:diva-281795DOI: 10.1002/chem.201504924ISI: 000370193000029PubMedID: 26791436OAI: oai:DiVA.org:uu-281795DiVA, id: diva2:915603
Forskningsfinansiär
Vetenskapsrådet, 621-2011-4177Tillgänglig från: 2016-03-30 Skapad: 2016-03-30 Senast uppdaterad: 2018-04-23Bibliografiskt granskad
Ingår i avhandling
1. Influence of Aromaticity on Excited State Structure, Reactivity and Properties
Öppna denna publikation i ny flik eller fönster >>Influence of Aromaticity on Excited State Structure, Reactivity and Properties
2018 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

This thesis describes work that could help development of new photochemical reactions and light-absorbing materials. Focus is on the chemical concept "aromaticity" which is a proven conceptual tool in developing thermal chemical reactions. It is here shown that aromaticity is also valuable for photochemistry. The influence of aromaticity is discussed in terms of structure, reactivity and properties. With regard to structure, it is found that photoexcited molecules change their structure to attain aromatic stabilization (planarize, allow through-space conjugation) or avoid antiaromatic destabilization (pucker). As for reactivity, it is found that stabilization/destabilization of reactants decrease/increase photoreactivity, in accordance with the Bell-Evans-Polanyi relationship. Two photoreactions based on excited state antiaromatic destabilization of the substrates are reported. Finally, with respect to properties, it is shown that excited state energies can be tuned by considering aromatic effects of both the electronic ground state and the electronically excited states. The fundamental research presented in this thesis forms a foundation for the development of new photochemical reactions and design of compounds for new organic electronic materials.

Ort, förlag, år, upplaga, sidor
Uppsala: Acta Universitatis Upsaliensis, 2018. s. 55
Serie
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1679
Nyckelord
photochemistry, aromaticity, computational chemistry
Nationell ämneskategori
Organisk kemi Teoretisk kemi
Forskningsämne
Kemi med inriktning mot organisk kemi
Identifikatorer
urn:nbn:se:uu:diva-349229 (URN)978-91-513-0354-3 (ISBN)
Disputation
2018-06-14, room 80101, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (Engelska)
Opponent
Handledare
Tillgänglig från: 2018-05-22 Skapad: 2018-04-23 Senast uppdaterad: 2018-09-27

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