Cargando…

Quest for the Most Aromatic Pathway in Charged Expanded Porphyrins

Despite the central role of aromaticity in the chemistry of expanded porphyrins, the evaluation of aromaticity remains difficult for these extended macrocycles. The presence of multiple conjugation pathways and different planar and nonplanar π‐conjugation topologies makes the quantification of globa...

Descripción completa

Detalles Bibliográficos
Autores principales: Casademont‐Reig, Irene, Woller, Tatiana, García, Victor, Contreras‐García, Julia, Tiznado, William, Torrent‐Sucarrat, Miquel, Matito, Eduard, Alonso, Mercedes
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10099525/
https://www.ncbi.nlm.nih.gov/pubmed/36194440
http://dx.doi.org/10.1002/chem.202202264
_version_ 1785025071049342976
author Casademont‐Reig, Irene
Woller, Tatiana
García, Victor
Contreras‐García, Julia
Tiznado, William
Torrent‐Sucarrat, Miquel
Matito, Eduard
Alonso, Mercedes
author_facet Casademont‐Reig, Irene
Woller, Tatiana
García, Victor
Contreras‐García, Julia
Tiznado, William
Torrent‐Sucarrat, Miquel
Matito, Eduard
Alonso, Mercedes
author_sort Casademont‐Reig, Irene
collection PubMed
description Despite the central role of aromaticity in the chemistry of expanded porphyrins, the evaluation of aromaticity remains difficult for these extended macrocycles. The presence of multiple conjugation pathways and different planar and nonplanar π‐conjugation topologies makes the quantification of global and local aromaticity even more challenging. In neutral expanded porphyrins, the predominance of the aromatic conjugation pathway passing through the imine‐type nitrogens and circumventing the amino NH groups is established. However, for charged macrocycles, the question about the main conjugation circuit remains open. Accordingly, different conjugation pathways in a set of neutral, anionic, and cationic expanded porphyrins were investigated by means of several aromaticity indices rooted in the structural, magnetic, and electronic criteria. Overall, our results reveal the predominance of the conjugation pathway that passes through all nitrogen atoms to describe the aromaticity of deprotonated expanded porphyrins, while the outer pathway through the perimeter carbon atoms becomes the most aromatic in protonated macrocycles. In nonplanar and charged macrocycles, a discrepancy between electronic and magnetic descriptors is observed. Nevertheless, our work demonstrates AV(min) remains the best tool to determine the main conjugation pathway of expanded porphyrins.
format Online
Article
Text
id pubmed-10099525
institution National Center for Biotechnology Information
language English
publishDate 2022
publisher John Wiley and Sons Inc.
record_format MEDLINE/PubMed
spelling pubmed-100995252023-04-14 Quest for the Most Aromatic Pathway in Charged Expanded Porphyrins Casademont‐Reig, Irene Woller, Tatiana García, Victor Contreras‐García, Julia Tiznado, William Torrent‐Sucarrat, Miquel Matito, Eduard Alonso, Mercedes Chemistry Research Articles Despite the central role of aromaticity in the chemistry of expanded porphyrins, the evaluation of aromaticity remains difficult for these extended macrocycles. The presence of multiple conjugation pathways and different planar and nonplanar π‐conjugation topologies makes the quantification of global and local aromaticity even more challenging. In neutral expanded porphyrins, the predominance of the aromatic conjugation pathway passing through the imine‐type nitrogens and circumventing the amino NH groups is established. However, for charged macrocycles, the question about the main conjugation circuit remains open. Accordingly, different conjugation pathways in a set of neutral, anionic, and cationic expanded porphyrins were investigated by means of several aromaticity indices rooted in the structural, magnetic, and electronic criteria. Overall, our results reveal the predominance of the conjugation pathway that passes through all nitrogen atoms to describe the aromaticity of deprotonated expanded porphyrins, while the outer pathway through the perimeter carbon atoms becomes the most aromatic in protonated macrocycles. In nonplanar and charged macrocycles, a discrepancy between electronic and magnetic descriptors is observed. Nevertheless, our work demonstrates AV(min) remains the best tool to determine the main conjugation pathway of expanded porphyrins. John Wiley and Sons Inc. 2022-11-28 2023-01-27 /pmc/articles/PMC10099525/ /pubmed/36194440 http://dx.doi.org/10.1002/chem.202202264 Text en © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Research Articles
Casademont‐Reig, Irene
Woller, Tatiana
García, Victor
Contreras‐García, Julia
Tiznado, William
Torrent‐Sucarrat, Miquel
Matito, Eduard
Alonso, Mercedes
Quest for the Most Aromatic Pathway in Charged Expanded Porphyrins
title Quest for the Most Aromatic Pathway in Charged Expanded Porphyrins
title_full Quest for the Most Aromatic Pathway in Charged Expanded Porphyrins
title_fullStr Quest for the Most Aromatic Pathway in Charged Expanded Porphyrins
title_full_unstemmed Quest for the Most Aromatic Pathway in Charged Expanded Porphyrins
title_short Quest for the Most Aromatic Pathway in Charged Expanded Porphyrins
title_sort quest for the most aromatic pathway in charged expanded porphyrins
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10099525/
https://www.ncbi.nlm.nih.gov/pubmed/36194440
http://dx.doi.org/10.1002/chem.202202264
work_keys_str_mv AT casademontreigirene questforthemostaromaticpathwayinchargedexpandedporphyrins
AT wollertatiana questforthemostaromaticpathwayinchargedexpandedporphyrins
AT garciavictor questforthemostaromaticpathwayinchargedexpandedporphyrins
AT contrerasgarciajulia questforthemostaromaticpathwayinchargedexpandedporphyrins
AT tiznadowilliam questforthemostaromaticpathwayinchargedexpandedporphyrins
AT torrentsucarratmiquel questforthemostaromaticpathwayinchargedexpandedporphyrins
AT matitoeduard questforthemostaromaticpathwayinchargedexpandedporphyrins
AT alonsomercedes questforthemostaromaticpathwayinchargedexpandedporphyrins