Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n + 2)π-Rings?

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Ayub, RabiaUppsala universitet,Molekylär biomimetik,Uppsala University, Sweden (author)

Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n + 2)π-Rings?

Article/chapterEnglish2017

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2017-06-07
American Chemical Society,2017
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LIBRIS-ID:oai:DiVA.org:ri-57308
https://urn.kb.se/resolve?urn=urn:nbn:se:ri:diva-57308URI
https://doi.org/10.1021/acs.joc.7b00906DOI
https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-329665URI

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Language:English
Summary in:English

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Subject category:art swepub-publicationtype

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Funding details: European Commission, EC; Funding details: Generalitat de Catalunya, 2014SGR931; Funding details: Ministerio de Economía y Competitividad, MINECO, CTQ2014-54306-P; Funding details: Institució Catalana de Recerca i Estudis Avançats, ICREA, 2014FI-B00429; Funding details: European Regional Development Fund, FEDER; Funding details: National Supercomputer Centre, Linköpings Universitet, NSC, SNIC-2016-1-74, SNIC-2016/7-21; Funding text 1: The Swedish Infrastructure for Computing (SNIC) at NSC and UPPMAX (Grants SNIC-2016-1-74 and SNIC-2016/7-21) are greatly acknowledged for the generous allotment of computer time. M.S. and O.E.B. acknowledge the Ministerio de Economia y Competitividad (MINECO) of Spain (Project CTQ2014-54306-P), the Generalitat de Catalunya (Project 2014SGR931, Xarxa de Referencia en Quimica Teorica i Computacional, ICREA Academia 2014 Prize for M.S. and Grant No. 2014FI-B00429 to O.E.B.), and the EU under the FEDER GrantUNGI10-4E-801 (European Fund for Regional Development).
Compounds that can be labeled as "aromatic chameleons" are π-conjugated compounds that are able to adjust their π-electron distributions so as to comply with the different rules of aromaticity in different electronic states. We used quantum chemical calculations to explore how the fusion of benzene rings onto aromatic chameleonic units represented by biphenylene, dibenzocyclooctatetraene, and dibenzo[a,e]pentalene modifies the first triplet excited states (T1) of the compounds. Decreases in T1 energies are observed when going from isomers with linear connectivity of the fused benzene rings to those with cis- or trans-bent connectivities. The T1 energies decreased down to those of the parent (isolated) 4nπ-electron units. Simultaneously, we observe an increased influence of triplet state aromaticity of the central 4n ring as given by Baird's rule and evidenced by geometric, magnetic, and electron density based aromaticity indices (HOMA, NICS-XY, ACID, and FLU). Because of an influence of triplet state aromaticity in the central 4nπ-electron units, the most stabilized compounds retain the triplet excitation in Baird π-quartets or octets, enabling the outer benzene rings to adapt closed-shell singlet Clar π-sextet character. Interestingly, the T1 energies go down as the total number of aromatic cycles within a molecule in the T1 state increases.

Subject headings and genre

NATURVETENSKAP Kemi Organisk kemi hsv//swe
NATURAL SCIENCES Chemical Sciences Organic Chemistry hsv//eng
Aromatization
Benzene
Electronic states
Electrons
Excited states
Isomers
Quantum chemistry
Aromaticities
Aromaticity indices
Closed shells
Electron distributions
Quantum chemical calculations
Triplet excitation
Triplet state
Triplet state energies
Quantum theory
hydrocarbon
polycyclic aromatic hydrocarbon derivative
Article
conjugation
electron
excitation
geometry
magnet

Added entries (persons, corporate bodies, meetings, titles ...)

Bakouri, O. E.Univ Girona, IQCC, C Maria Aurelia Capmany 6, Girona 17003, Catalonia, Spain. (author)
Jorner, KjellUppsala universitet,Molekylär biomimetik(Swepub:uu)kjejo447 (author)
Solà, M.Univ Girona, IQCC, C Maria Aurelia Capmany 6, Girona 17003, Catalonia, Spain. (author)
Ottosson, HenrikUppsala universitet,Molekylär biomimetik(Swepub:uu)heott255 (author)
Uppsala universitetMolekylär biomimetik (creator_code:org_t)

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In:Journal of Organic Chemistry: American Chemical Society82:12, s. 6327-63400022-32631520-6904

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By the author/editor: Ayub, Rabia; Bakouri, O. E.; Jorner, Kjell; Solà, M.; Ottosson, Henrik

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