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

Show simple item record

dc.contributor.author Pareras, Gerard
dc.contributor.author Szczepanik, Dariusz Wojciech
dc.contributor.author Duran, Miquel
dc.contributor.author Solà, Miquel
dc.contributor.author Simon, Silvia
dc.date.accessioned 2019-12-18T11:43:32Z
dc.date.available 2019-12-18T11:43:32Z
dc.date.issued 2019-11-06
dc.identifier.citation Pareras, 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.9b02526 en
dc.identifier.volume 84 en
dc.identifier.issued 23 en
dc.identifier.startpage 15538 en
dc.identifier.endpage 15548 en
dc.identifier.issn 0022-3263
dc.identifier.uri http://hdl.handle.net/10468/9436
dc.identifier.doi 10.1021/acs.joc.9b02526 en
dc.description.abstract The 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.sponsorship Ministerio 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.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher ACS Publications en
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.9b02526 en
dc.subject Hydrogen bond en
dc.subject Resonance-assisted hydrogen bonds en
dc.subject RAHB en
dc.subject Aromaticity en
dc.title Tuning the strength of the resonance-assisted hydrogen bond in acenes and phenacenes with two o-hydroxyaldehyde groups - The importance of topology en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother Gerard Pareras, Tyndall National Institute, University College Cork, Cork, Ireland. T: +353-21-490-3000 E: gerard.pareras@tyndall.ie en
dc.internal.availability Full text available en
dc.check.info Access to this article is restricted until 12 months after publication by request of the publisher. en
dc.check.date 2020-11-06
dc.date.updated 2019-11-14T11:15:30Z
dc.description.version Accepted Version en
dc.internal.rssid 499913294
dc.contributor.funder Ministerio de Economía, Industria y Competitividad, Gobierno de España en
dc.contributor.funder Departament d'Innovació, Universitats i Empresa, Generalitat de Catalunya en
dc.contributor.funder European Regional Development Fund en
dc.contributor.funder Narodowe Centrum Nauki en
dc.description.status Peer reviewed en
dc.identifier.journaltitle Journal of Organic Chemistry en
dc.internal.copyrightchecked Yes
dc.internal.licenseacceptance Yes en
dc.internal.IRISemailaddress gerard.pareras@tyndall.ie en
dc.identifier.eissn 1520-6904


Files in this item

This item appears in the following Collection(s)

Show simple item record

This website uses cookies. By using this website, you consent to the use of cookies in accordance with the UCC Privacy and Cookies Statement. For more information about cookies and how you can disable them, visit our Privacy and Cookies statement