uu.seUppsala University Publications
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Analysis of a Compound Class with Triplet States Stabilized by Potentially Baird Aromatic [10]Annulenyl Dicationic Rings
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
Univ Girona, IQCC, Campus Montilivi S-N, Girona 17071, Catalonia, Spain.;Univ Girona, Dept Quim, Campus Montilivi S-N, Girona 17071, Catalonia, Spain..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - BMC, Physical Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry. Uppsala Univ, Uppsala Ctr Computat Chem UC3, Box 518, S-75120 Uppsala, Sweden..
Show others and affiliations
2016 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 22, no 8, p. 2793-2800Article in journal (Refereed) Published
Resource type
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.

Place, publisher, year, edition, pages
2016. Vol. 22, no 8, p. 2793-2800
Keywords [en]
annulenes, aromaticity, Baird's rule, diradical species, electronic structure
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-281795DOI: 10.1002/chem.201504924ISI: 000370193000029PubMedID: 26791436OAI: oai:DiVA.org:uu-281795DiVA, id: diva2:915603
Funder
Swedish Research Council, 621-2011-4177Available from: 2016-03-30 Created: 2016-03-30 Last updated: 2018-04-23Bibliographically approved
In thesis
1. Influence of Aromaticity on Excited State Structure, Reactivity and Properties
Open this publication in new window or tab >>Influence of Aromaticity on Excited State Structure, Reactivity and Properties
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
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.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2018. p. 55
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1679
Keywords
photochemistry, aromaticity, computational chemistry
National Category
Organic Chemistry Theoretical Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-349229 (URN)978-91-513-0354-3 (ISBN)
Public defence
2018-06-14, room 80101, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2018-05-22 Created: 2018-04-23 Last updated: 2018-05-22

Open Access in DiVA

No full text in DiVA

Other links

Publisher's full textPubMed

Authority records BETA

Jorner, KjellAyub, RabiaLindh, RolandOttosson, Henrik

Search in DiVA

By author/editor
Jorner, KjellAyub, RabiaLindh, RolandOttosson, Henrik
By organisation
Physical Organic ChemistryTheoretical Chemistry
In the same journal
Chemistry - A European Journal
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar

doi
pubmed
urn-nbn

Altmetric score

doi
pubmed
urn-nbn
Total: 615 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf