Exploiting molecular self-assembly: From urea-based organocatalysts to multifunctional supramolecular gels

We describe the self-assembly properties of chiral N,N′-disubstituted urea-based organocatalyst 1 that leads to the formation of hierarchical supramolecular gels in organic solvents at low concentrations. The major driving forces for the gelation are hydrogen bonding and π-π interactions according t...

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Detalhes bibliográficos
Autores: Schön, Eva-Maria, Marqués-López, Eugenia, Herrera, Raquel P., Alemán, Carlos, Díaz Díaz, David
Tipo de documento: artigo
Estado:Versión aceptada para publicación
Data de publicação:2014
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositório:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/111771
Acesso em linha:http://hdl.handle.net/10261/111771
Access Level:Acceso aberto
Palavra-chave:Multistimuli responsiveness
Organogels
Self-assembly
Ureas
Multifunctional materials
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spelling Exploiting molecular self-assembly: From urea-based organocatalysts to multifunctional supramolecular gelsSchön, Eva-MariaMarqués-López, EugeniaHerrera, Raquel P.Alemán, CarlosDíaz Díaz, DavidMultistimuli responsivenessOrganogelsSelf-assemblyUreasMultifunctional materialsWe describe the self-assembly properties of chiral N,N′-disubstituted urea-based organocatalyst 1 that leads to the formation of hierarchical supramolecular gels in organic solvents at low concentrations. The major driving forces for the gelation are hydrogen bonding and π-π interactions according to FTIR and 1H NMR spectroscopy, as well as quantum-mechanical studies. The gelation scope could be interpreted based on Kamlet-Taft solvatochromic parameters. TEM, SEM, and AFM imaging revealed that a variety of morphologies including helical, laths, porous, and lamellar nanostructures could be obtained by varying the solvent. Experimental gelation tests and computational structural analysis of various structurally related compounds proved the existence of a unique set of molecular interactions and an optimal hydrophilic/hydrophobic balance in 1 that drive the formation of stable gels. Responses to thermal, mechanical, optical, and chemical stimuli, as well as multifunctionality were demonstrated in some model gel materials. Specifically, 1 could be used for the phase-selective gelation of organic solvent/water mixtures. The gel prepared in glycerol was found to be thixotropic and provided a sensitive colorimetric method for the detection of Ag I ions at millimolar concentrations in aqueous solution. Moreover, the gel matrix obtained in toluene served as a nanoreactor for the Friedel-Crafts alkylation of 1H-indole with trans-β-nitrostyrene.Financial support from the Universität Regensburg (Förderlinie C des Finanziellen Anreizsystems für Drittmitteleinwerbung), Spanish Ministry of Economía y Competitividad (MINECO, Madrid, Spain, Projects CTQ2010–19606 and MAT2012–34498), and the Governments of Aragón (Zaragoza, Spain, Research Group E-10) and Catalunya (research group 2009 SGR 925, XRQTC and “ICREA Academia” Award for excellence in research to C.A.) is gratefully acknowledged.Peer ReviewedWiley-VCHUniversity of RegensburgARAID FoundationMinisterio de Economía y Competitividad (España)Gobierno de AragónInstitución Catalana de Investigación y Estudios AvanzadosEuropean CommissionConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2015201520142015info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/111771reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Ingléshttp://dx.doi.org/10.1002/chem.201402436Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/1117712026-05-22T06:33:51Z
dc.title.none.fl_str_mv Exploiting molecular self-assembly: From urea-based organocatalysts to multifunctional supramolecular gels
title Exploiting molecular self-assembly: From urea-based organocatalysts to multifunctional supramolecular gels
spellingShingle Exploiting molecular self-assembly: From urea-based organocatalysts to multifunctional supramolecular gels
Schön, Eva-Maria
Multistimuli responsiveness
Organogels
Self-assembly
Ureas
Multifunctional materials
title_short Exploiting molecular self-assembly: From urea-based organocatalysts to multifunctional supramolecular gels
title_full Exploiting molecular self-assembly: From urea-based organocatalysts to multifunctional supramolecular gels
title_fullStr Exploiting molecular self-assembly: From urea-based organocatalysts to multifunctional supramolecular gels
title_full_unstemmed Exploiting molecular self-assembly: From urea-based organocatalysts to multifunctional supramolecular gels
title_sort Exploiting molecular self-assembly: From urea-based organocatalysts to multifunctional supramolecular gels
dc.creator.none.fl_str_mv Schön, Eva-Maria
Marqués-López, Eugenia
Herrera, Raquel P.
Alemán, Carlos
Díaz Díaz, David
author Schön, Eva-Maria
author_facet Schön, Eva-Maria
Marqués-López, Eugenia
Herrera, Raquel P.
Alemán, Carlos
Díaz Díaz, David
author_role author
author2 Marqués-López, Eugenia
Herrera, Raquel P.
Alemán, Carlos
Díaz Díaz, David
author2_role author
author
author
author
dc.contributor.none.fl_str_mv University of Regensburg
ARAID Foundation
Ministerio de Economía y Competitividad (España)
Gobierno de Aragón
Institución Catalana de Investigación y Estudios Avanzados
European Commission
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Multistimuli responsiveness
Organogels
Self-assembly
Ureas
Multifunctional materials
topic Multistimuli responsiveness
Organogels
Self-assembly
Ureas
Multifunctional materials
description We describe the self-assembly properties of chiral N,N′-disubstituted urea-based organocatalyst 1 that leads to the formation of hierarchical supramolecular gels in organic solvents at low concentrations. The major driving forces for the gelation are hydrogen bonding and π-π interactions according to FTIR and 1H NMR spectroscopy, as well as quantum-mechanical studies. The gelation scope could be interpreted based on Kamlet-Taft solvatochromic parameters. TEM, SEM, and AFM imaging revealed that a variety of morphologies including helical, laths, porous, and lamellar nanostructures could be obtained by varying the solvent. Experimental gelation tests and computational structural analysis of various structurally related compounds proved the existence of a unique set of molecular interactions and an optimal hydrophilic/hydrophobic balance in 1 that drive the formation of stable gels. Responses to thermal, mechanical, optical, and chemical stimuli, as well as multifunctionality were demonstrated in some model gel materials. Specifically, 1 could be used for the phase-selective gelation of organic solvent/water mixtures. The gel prepared in glycerol was found to be thixotropic and provided a sensitive colorimetric method for the detection of Ag I ions at millimolar concentrations in aqueous solution. Moreover, the gel matrix obtained in toluene served as a nanoreactor for the Friedel-Crafts alkylation of 1H-indole with trans-β-nitrostyrene.
publishDate 2014
dc.date.none.fl_str_mv 2014
2015
2015
2015
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Postprint
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/111771
url http://hdl.handle.net/10261/111771
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv http://dx.doi.org/10.1002/chem.201402436
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Wiley-VCH
publisher.none.fl_str_mv Wiley-VCH
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15.81155

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