Tuning the strength of the resonance-assisted hydrogen bond in acenes and phenacenes with two o-hydroxyaldehyde groups - The importance of topology

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dc.check.date2020-11-06
dc.check.infoAccess to this article is restricted until 12 months after publication by request of the publisher.en
dc.contributor.authorPareras, Gerard
dc.contributor.authorSzczepanik, Dariusz Wojciech
dc.contributor.authorDuran, Miquel
dc.contributor.authorSolà, Miquel
dc.contributor.authorSimon, Silvia
dc.contributor.funderMinisterio de Economía, Industria y Competitividad, Gobierno de Españaen
dc.contributor.funderDepartament d'Innovació, Universitats i Empresa, Generalitat de Catalunyaen
dc.contributor.funderEuropean Regional Development Funden
dc.contributor.funderNarodowe Centrum Naukien
dc.date.accessioned2019-12-18T11:43:32Z
dc.date.available2019-12-18T11:43:32Z
dc.date.issued2019-11-06
dc.date.updated2019-11-14T11:15:30Z
dc.description.abstractThe fact that intramolecular resonance-assisted hydrogen bonds (RAHBs) are stronger than conventional ones is attributed to the partial delocalization of the π-electrons within the hydrogen bond (HB) motif, the so-called quasi-ring. If an aromatic ring is involved in the formation of the RAHB, previous studies have shown that there is an interplay between aromaticity and HB strength. Moreover, in 1,3-dihydroxyaryl-2-aldehydes, some of us found that the position of the quasi-ring formed by the substituents interacting through RAHB influences the strength of the H bonding, the HBs being stronger when a kinked-like structure is generated by formation of the quasi-ring. In this work, we explore this concept further by considering a set of acenes and phenacenes of different sizes with two o-hydroxyaldehyde substituents. Calculations with the CAM-B3LYP/6-311++G(d,p) + GD3B method show that for long acenes or phenacenes, once the substituent effect loses importance because quasi-rings are pulled apart far from each other, the different topologies rule the HB distances. This fact can be explained in most cases using an extended Clar’s aromatic π-sextet model. In some kinked systems, however, the justification from the Clar model has to be complemented by taking into account the repulsion between hydrogen atoms. Triphenylene-like compounds with different numbers of benzene rings have been studied, finding out a very good relationship between aromaticity of the ipso- and quasi-rings with the RAHB distances. This result confirms the importance of the communication of the π-systems of the ipso- and quasi-rings.en
dc.description.sponsorshipMinisterio de Economía, Industria y Competitividad, Gobierno de España (CTQ2017-85341-P); Departament d'Innovació, Universitats i Empresa, Generalitat de Catalunya (2017-SGR-39, XRQTC, and ICREA Academia 2014 Award); European Regional Development Fund (UNGI10-4E-801); Narodowe Centrum Nauki (Sonata Project 2015/17/D/ST4/00558)en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationPareras, G., Szczepanik, D. W., Duran, M., Solà, M. and Simon, S. (2019) 'Tuning the strength of the resonance-assisted hydrogen bond in acenes and phenacenes with two o-hydroxyaldehyde groups - The importance of topology', Journal of Organic Chemistry, 84(23), pp. 15538-15548. doi: 10.1021/acs.joc.9b02526en
dc.identifier.doi10.1021/acs.joc.9b02526en
dc.identifier.eissn1520-6904
dc.identifier.endpage15548en
dc.identifier.issn0022-3263
dc.identifier.issued23en
dc.identifier.journaltitleJournal of Organic Chemistryen
dc.identifier.startpage15538en
dc.identifier.urihttps://hdl.handle.net/10468/9436
dc.identifier.volume84en
dc.language.isoenen
dc.publisherACS Publicationsen
dc.rights© 2019, American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, copyright © American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.joc.9b02526en
dc.subjectHydrogen bonden
dc.subjectResonance-assisted hydrogen bondsen
dc.subjectRAHBen
dc.subjectAromaticityen
dc.titleTuning the strength of the resonance-assisted hydrogen bond in acenes and phenacenes with two o-hydroxyaldehyde groups - The importance of topologyen
dc.typeArticle (peer-reviewed)en
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