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
dc.date.accessioned
2020-01-07T10:40:24Z
dc.date.available
2021-04-07T08:03:01Z
dc.date.issued
2019-11-06
dc.identifier.issn
0022-3263
dc.identifier.uri
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 pi-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 pull 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 pi-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 number 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 pi-systems of the ipso- and quasi-rings
dc.description.sponsorship
We are grateful for financial support from the Spanish MINECO (CTQ2017-85341-P) and
the Catalan DIUE (2017-SGR-39, XRQTC, and ICREA Academia 2014 Award to M.S.)
and the FEDER fund (UNGI10-4E-801)
dc.format.extent
11 p.
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
© American Chemical Society (ACS)
dc.relation
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-85341-P/ES/AVANCES EN LA REACTIVIDAD DE FULLERENOS Y NANOTUBOS: ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION/
dc.relation.isformatof
Versió postprint del document publicat a: https://doi.org/10.1021/acs.joc.9b02526
dc.relation.ispartof
© Journal of Organic Chemistry, 2019, vol. 84, núm. 23, p. 15538-15548
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.source
Pareras, Gerard Szczepanik, Dariusz W. Duran i Portas, Miquel Solà i Puig, Miquel Simon i Rabasseda, Sílvia 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 15538 15548
dc.subject
dc.title
Tuning the strength of the resonance-assisted hydrogen bond in acenes and phenacenes with two o-hydroxyaldehyde groups: the importance of topology
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.embargo.terms
2020-11-06T00:00:00Z
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2020-11-06
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
030516
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-6904