Tuning the strength of the resonance-assisted hydrogen bond in acenes and phenacenes with two o-hydroxyaldehyde groups - The importance of topology
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.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.date.accessioned | 2019-12-18T11:43:32Z | |
dc.date.available | 2019-12-18T11:43:32Z | |
dc.date.issued | 2019-11-06 | |
dc.date.updated | 2019-11-14T11:15:30Z | |
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.description.status | Peer reviewed | en |
dc.description.version | Accepted Version | en |
dc.format.mimetype | application/pdf | en |
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.doi | 10.1021/acs.joc.9b02526 | en |
dc.identifier.eissn | 1520-6904 | |
dc.identifier.endpage | 15548 | en |
dc.identifier.issn | 0022-3263 | |
dc.identifier.issued | 23 | en |
dc.identifier.journaltitle | Journal of Organic Chemistry | en |
dc.identifier.startpage | 15538 | en |
dc.identifier.uri | https://hdl.handle.net/10468/9436 | |
dc.identifier.volume | 84 | 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 |
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