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

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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