The key role of chirality and peripheral substitution in the columnar organization of bowl-shaped subphthalocyanines

The columnar arrangement of bowl-shaped aromatics is a promising strategy for producing high-performing semiconductors. However, the structural factors that dictate the self-assembly of these molecules remain poorly understood. Herein, we show how chirality and peripheral substitution affect the col...

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Autores: Labella Santodomingo, Jorge, López-Serrano, Elisa, Aranda, Daniel, Mayoral Muñoz, María José, Ortí, Enrique, Torres Cebada, Tomás
Tipo de recurso: artículo
Fecha de publicación:2024
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/714893
Acceso en línea:http://hdl.handle.net/10486/714893
https://dx.doi.org/10.1039/d4sc03976a
Access Level:acceso abierto
Palabra clave:Subphthalocyanines
Stereochemistry
Molecular Dynamics
Columnar assembly
Química
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spelling The key role of chirality and peripheral substitution in the columnar organization of bowl-shaped subphthalocyaninesLabella Santodomingo, JorgeLópez-Serrano, ElisaAranda, DanielMayoral Muñoz, María JoséOrtí, EnriqueTorres Cebada, TomásSubphthalocyaninesStereochemistryMolecular DynamicsColumnar assemblyQuímicaThe columnar arrangement of bowl-shaped aromatics is a promising strategy for producing high-performing semiconductors. However, the structural factors that dictate the self-assembly of these molecules remain poorly understood. Herein, we show how chirality and peripheral substitution affect the columnar assembly of subphthalocyanines (SubPcs) in solution. Both aspects are found to influence the structure, stability, and formation mechanism of the supramolecular polymer obtained. Whereas enantiopure tri-substituted SubPcs cooperatively polymerize into homochiral head-to-tail arrays, racemic mixtures socially self-sort, leading to heterochiral columnar polymers. In sharp contrast, hexa-substituted SubPcs polymerize following an isodesmic mechanism, producing highly robust columnar systems. As elucidated by molecular dynamics calculations, the conformational flexibility of these SubPcs, as well as the number of peripheral groups able to intermolecularly interact, underlie these significant differences. The results presented herein pave the way for the realistic application of bowl-shaped π-compoundsFinancial support from the Spanish MCIN/AEI (Projects PID2020-116490GB-I00, PID2021-128569NB-I00, TED2021131255B-C43 and C44, and CEX2019-000919-M, funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”), the Comunidad de Madrid (MAD2D-CM (UAM1)-MRR), the Generalitat Valenciana (MFA/2022/017) is fully acknowledged. The MAD2D-CM (UAM1)-MRR and MFA/ 2022/017 projects are part of the Advanced Materials programme supported by the MCIN with funding from the European Union NextGenerationEU (PRTR-C17.I1) and by the Comunidad de Madrid and Generalitat Valenciana, respectively. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686). T. T. also acknowledges the Alexander von Humboldt Foundation (Germany) for the A. v. Humboldt– J. C. Mutis Research Award 2023 (ref. 3.3– 1231125– ESP-GSA). J. L. and E. L. acknowledges MECD, Spain, fora F. P. U. fellowshipRoyal Society of ChemistryDepartamento de Química OrgánicaFacultad de Ciencias20242024-07-29research articlehttp://purl.org/coar/resource_type/c_2df8fbb1VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/714893https://dx.doi.org/10.1039/d4sc03976areponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/7148932026-06-23T12:46:27Z
dc.title.none.fl_str_mv The key role of chirality and peripheral substitution in the columnar organization of bowl-shaped subphthalocyanines
title The key role of chirality and peripheral substitution in the columnar organization of bowl-shaped subphthalocyanines
spellingShingle The key role of chirality and peripheral substitution in the columnar organization of bowl-shaped subphthalocyanines
Labella Santodomingo, Jorge
Subphthalocyanines
Stereochemistry
Molecular Dynamics
Columnar assembly
Química
title_short The key role of chirality and peripheral substitution in the columnar organization of bowl-shaped subphthalocyanines
title_full The key role of chirality and peripheral substitution in the columnar organization of bowl-shaped subphthalocyanines
title_fullStr The key role of chirality and peripheral substitution in the columnar organization of bowl-shaped subphthalocyanines
title_full_unstemmed The key role of chirality and peripheral substitution in the columnar organization of bowl-shaped subphthalocyanines
title_sort The key role of chirality and peripheral substitution in the columnar organization of bowl-shaped subphthalocyanines
dc.creator.none.fl_str_mv Labella Santodomingo, Jorge
López-Serrano, Elisa
Aranda, Daniel
Mayoral Muñoz, María José
Ortí, Enrique
Torres Cebada, Tomás
author Labella Santodomingo, Jorge
author_facet Labella Santodomingo, Jorge
López-Serrano, Elisa
Aranda, Daniel
Mayoral Muñoz, María José
Ortí, Enrique
Torres Cebada, Tomás
author_role author
author2 López-Serrano, Elisa
Aranda, Daniel
Mayoral Muñoz, María José
Ortí, Enrique
Torres Cebada, Tomás
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Departamento de Química Orgánica
Facultad de Ciencias
dc.subject.none.fl_str_mv Subphthalocyanines
Stereochemistry
Molecular Dynamics
Columnar assembly
Química
topic Subphthalocyanines
Stereochemistry
Molecular Dynamics
Columnar assembly
Química
description The columnar arrangement of bowl-shaped aromatics is a promising strategy for producing high-performing semiconductors. However, the structural factors that dictate the self-assembly of these molecules remain poorly understood. Herein, we show how chirality and peripheral substitution affect the columnar assembly of subphthalocyanines (SubPcs) in solution. Both aspects are found to influence the structure, stability, and formation mechanism of the supramolecular polymer obtained. Whereas enantiopure tri-substituted SubPcs cooperatively polymerize into homochiral head-to-tail arrays, racemic mixtures socially self-sort, leading to heterochiral columnar polymers. In sharp contrast, hexa-substituted SubPcs polymerize following an isodesmic mechanism, producing highly robust columnar systems. As elucidated by molecular dynamics calculations, the conformational flexibility of these SubPcs, as well as the number of peripheral groups able to intermolecularly interact, underlie these significant differences. The results presented herein pave the way for the realistic application of bowl-shaped π-compounds
publishDate 2024
dc.date.none.fl_str_mv 2024
2024-07-29
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10486/714893
https://dx.doi.org/10.1039/d4sc03976a
url http://hdl.handle.net/10486/714893
https://dx.doi.org/10.1039/d4sc03976a
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.812455

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