Three-Dimensional Fully pi-Conjugated Macrocycles: When 3D-Aromatic and when 2D-Aromatic-in-3D?

Several fully pi-conjugated macrocycles with puckered or cage-type structures were recently found to exhibit aromatic character according to both experiments and computations. We examine their electronic structures and put them in relation to 3D-aromatic molecules (e.g., closo-boranes) and to 2D-aro...

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Detalles Bibliográficos
Autores: El Bakouri, Ouissam, Szczepanik, Dariusz W., Jorner, Kjell, Ayub, Rabia, Bultinck, Patrick, Solà i Puig, Miquel, Ottosson, Henrik
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2022
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/21205
Acceso en línea:http://hdl.handle.net/10256/21205
Access Level:acceso abierto
Palabra clave:Química quàntica
Quantum chemistry
Aromaticitat (Química)
Aromaticity (Chemistry)
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spelling Three-Dimensional Fully pi-Conjugated Macrocycles: When 3D-Aromatic and when 2D-Aromatic-in-3D?El Bakouri, OuissamSzczepanik, Dariusz W.Jorner, KjellAyub, RabiaBultinck, PatrickSolà i Puig, MiquelOttosson, HenrikQuímica quànticaQuantum chemistryAromaticitat (Química)Aromaticity (Chemistry)Several fully pi-conjugated macrocycles with puckered or cage-type structures were recently found to exhibit aromatic character according to both experiments and computations. We examine their electronic structures and put them in relation to 3D-aromatic molecules (e.g., closo-boranes) and to 2D-aromatic polycyclic aromatic hydrocarbons. Using qualitative theory combined with quantum chemical calculations, we find that the macrocycles explored hitherto should be described as 2D-aromatic with three-dimensional molecular structures (abbr. 2D-aromatic-in-3D) and not as truly 3D-aromatic. 3D-aromatic molecules have highly symmetric structures (or nearly so), leading to (at least) triply degenerate molecular orbitals, and for tetrahedral or octahedral molecules an aromatic closed-shell electronic structure with 6n + 2 electrons. Conversely, 2D-aromatic-in-3D structures exhibit aromaticity that results from the fulfillment of Hückel's 4n + 2 rule for each macrocyclic path, yet, their -electron counts are coincidentally 6n + 2 numbers for macrocycles with three tethers of equal lengths. It is notable that 2D-aromatic-in-3D macrocyclic cages can be aromatic with tethers of different lengths, i.e., with p-electron counts different from 6n + 2, and they are related to naphthalene. Finally, we identify tetrahedral and cubic pi-conjugated molecules that fulfill the 6n + 2 rule and exhibit significant electron delocalization. Yet, their properties resemble those of analogous compounds with electron counts that differ from 6n + 2. Thus, despite that these molecules show substantial pi-electron delocalization they cannot be classified as true 3D-aromaticsO.E.B. is grateful to the Wenner-Gren Foundations for a postdoctoral fellowship (UPD 2018-0305), and H.O., K.J., and R.A. acknowledge the Swedish Research Council for financial support (grants 2015-04538 and 2019-05618). M.S. is grateful for the financial support from the Spanish MICINN (project PID2020-113711GB-I00) and the Catalan DIUE (project 2017SGR39). D.W.S. acknowledges the financial support by the National Science Centre, Poland (2021/42/E/ST4/ 00332) and the PL-Grid Infrastructure of the Academic Computer Centre (CYFRONET). The computations were enabled by resources provided by the Swedish National Infrastructure for Computing (SNIC) at the National Supercomputer Center (NSC), Linköping, partially funded by the Swedish Research Council through grants 2015-04538 and 2019-05618American Chemical Society (ACS)Agencia Estatal de Investigación2022info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionpeer-reviewed16 p.application/pdfhttp://hdl.handle.net/10256/21205Journal of the American Chemical Society, 2022, vol. 144, núm. 19, p. 8560-8575Articles publicats (D-Q)El Bakouri, Ouissam Szczepanik, Dariusz W. Jorner, Kjell Ayub, Rabia Bultinck, Patrick Solà i Puig, Miquel Ottosson, Henrik 2022 Three-Dimensional Fully pi-Conjugated Macrocycles: When 3D-Aromatic and when 2D-Aromatic-in-3D? Journal of the American Chemical Society 144 19 8560 8575reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.1c13478info:eu-repo/semantics/altIdentifier/issn/0002-7863info:eu-repo/semantics/altIdentifier/eissn/1520-5126info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113711GB-I00Reconeixement 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0info:eu-repo/semantics/openAccessoai:recercat.cat:10256/212052026-05-29T05:05:01Z
dc.title.none.fl_str_mv Three-Dimensional Fully pi-Conjugated Macrocycles: When 3D-Aromatic and when 2D-Aromatic-in-3D?
title Three-Dimensional Fully pi-Conjugated Macrocycles: When 3D-Aromatic and when 2D-Aromatic-in-3D?
spellingShingle Three-Dimensional Fully pi-Conjugated Macrocycles: When 3D-Aromatic and when 2D-Aromatic-in-3D?
El Bakouri, Ouissam
Química quàntica
Quantum chemistry
Aromaticitat (Química)
Aromaticity (Chemistry)
title_short Three-Dimensional Fully pi-Conjugated Macrocycles: When 3D-Aromatic and when 2D-Aromatic-in-3D?
title_full Three-Dimensional Fully pi-Conjugated Macrocycles: When 3D-Aromatic and when 2D-Aromatic-in-3D?
title_fullStr Three-Dimensional Fully pi-Conjugated Macrocycles: When 3D-Aromatic and when 2D-Aromatic-in-3D?
title_full_unstemmed Three-Dimensional Fully pi-Conjugated Macrocycles: When 3D-Aromatic and when 2D-Aromatic-in-3D?
title_sort Three-Dimensional Fully pi-Conjugated Macrocycles: When 3D-Aromatic and when 2D-Aromatic-in-3D?
dc.creator.none.fl_str_mv El Bakouri, Ouissam
Szczepanik, Dariusz W.
Jorner, Kjell
Ayub, Rabia
Bultinck, Patrick
Solà i Puig, Miquel
Ottosson, Henrik
author El Bakouri, Ouissam
author_facet El Bakouri, Ouissam
Szczepanik, Dariusz W.
Jorner, Kjell
Ayub, Rabia
Bultinck, Patrick
Solà i Puig, Miquel
Ottosson, Henrik
author_role author
author2 Szczepanik, Dariusz W.
Jorner, Kjell
Ayub, Rabia
Bultinck, Patrick
Solà i Puig, Miquel
Ottosson, Henrik
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación
dc.subject.none.fl_str_mv Química quàntica
Quantum chemistry
Aromaticitat (Química)
Aromaticity (Chemistry)
topic Química quàntica
Quantum chemistry
Aromaticitat (Química)
Aromaticity (Chemistry)
description Several fully pi-conjugated macrocycles with puckered or cage-type structures were recently found to exhibit aromatic character according to both experiments and computations. We examine their electronic structures and put them in relation to 3D-aromatic molecules (e.g., closo-boranes) and to 2D-aromatic polycyclic aromatic hydrocarbons. Using qualitative theory combined with quantum chemical calculations, we find that the macrocycles explored hitherto should be described as 2D-aromatic with three-dimensional molecular structures (abbr. 2D-aromatic-in-3D) and not as truly 3D-aromatic. 3D-aromatic molecules have highly symmetric structures (or nearly so), leading to (at least) triply degenerate molecular orbitals, and for tetrahedral or octahedral molecules an aromatic closed-shell electronic structure with 6n + 2 electrons. Conversely, 2D-aromatic-in-3D structures exhibit aromaticity that results from the fulfillment of Hückel's 4n + 2 rule for each macrocyclic path, yet, their -electron counts are coincidentally 6n + 2 numbers for macrocycles with three tethers of equal lengths. It is notable that 2D-aromatic-in-3D macrocyclic cages can be aromatic with tethers of different lengths, i.e., with p-electron counts different from 6n + 2, and they are related to naphthalene. Finally, we identify tetrahedral and cubic pi-conjugated molecules that fulfill the 6n + 2 rule and exhibit significant electron delocalization. Yet, their properties resemble those of analogous compounds with electron counts that differ from 6n + 2. Thus, despite that these molecules show substantial pi-electron delocalization they cannot be classified as true 3D-aromatics
publishDate 2022
dc.date.none.fl_str_mv 2022
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
peer-reviewed
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/21205
url http://hdl.handle.net/10256/21205
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.1c13478
info:eu-repo/semantics/altIdentifier/issn/0002-7863
info:eu-repo/semantics/altIdentifier/eissn/1520-5126
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113711GB-I00
dc.rights.none.fl_str_mv Reconeixement 4.0 Internacional
http://creativecommons.org/licenses/by/4.0
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Reconeixement 4.0 Internacional
http://creativecommons.org/licenses/by/4.0
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 16 p.
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society (ACS)
publisher.none.fl_str_mv American Chemical Society (ACS)
dc.source.none.fl_str_mv Journal of the American Chemical Society, 2022, vol. 144, núm. 19, p. 8560-8575
Articles publicats (D-Q)
El Bakouri, Ouissam Szczepanik, Dariusz W. Jorner, Kjell Ayub, Rabia Bultinck, Patrick Solà i Puig, Miquel Ottosson, Henrik 2022 Three-Dimensional Fully pi-Conjugated Macrocycles: When 3D-Aromatic and when 2D-Aromatic-in-3D? Journal of the American Chemical Society 144 19 8560 8575
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,81155

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