Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure

Ditopic bis-pyrazolylpyridine ligands usually react with divalent metal ions (M2+) to produce dinuclear triple-stranded helicates [M2L3]4+ or, via π⋯π interactions, dimers of monoatomic complexes ([ML3]2)4+. The introduction of an additional benzene ring at each end of ligand L increases the number...

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Authors: Risa, Arnau, Barrios, Leoní A., Diego, Rosa, Roubeau, Olivier, Aleshin, Dmitry Y., Nelyubina, Yulia, Novikov, Valentin, Teat, Simon J., Ribas-Ariño, Jordi, Aromí, Guillem
Format: article
Status:Published version
Publication Date:2024
Country:España
Institution:Consejo Superior de Investigaciones Científicas (CSIC)
Repository:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/371016
Online Access:http://hdl.handle.net/10261/371016
Access Level:Open access
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spelling Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structureRisa, ArnauBarrios, Leoní A.Diego, RosaRoubeau, OlivierAleshin, Dmitry Y.Nelyubina, YuliaNovikov, ValentinTeat, Simon J.Ribas-Ariño, JordiAromí, GuillemDitopic bis-pyrazolylpyridine ligands usually react with divalent metal ions (M2+) to produce dinuclear triple-stranded helicates [M2L3]4+ or, via π⋯π interactions, dimers of monoatomic complexes ([ML3]2)4+. The introduction of an additional benzene ring at each end of ligand L increases the number of aromatic contacts within the supramolecular aggregate by 40%, driving the self-recognition process in an irreversible manner. Consequently, the mixing of new bis-pyrazolylquinoline L2 with FeX2 salts leads to crystallization of the tripartite high-spin assemblies (X@[Fe(L2)3]2)3+ (X = Cl, Br or I). The aggregates exhibit exceptional stability, as confirmed by a combination of paramagnetic 1H NMR techniques, demonstrating their persistence in solution. Our investigations further reveal that the guests Br− and I− are retained inside the associate in solution but Cl− is immediately released, resulting in the formation of the empty supramolecular dimer ([Fe(L2)3]2)4+.This research was supported by the Spanish Ministry of Science (TED2021-129214B-I00, PID2022-137764OB-I00, PID2020-118329RB-I00, BG22/00039 and PRTR-C17.I1), the Aragón Government (E31_23R PLATON) and used resources of the ALBA Synchrotron and of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DEAC02-05CH11231. Yu. N. and V. N. acknowledges the support of the Ministry of Science and Higher Education of the Russian Federation (grant no. 075-15-2020-779). G. A. thanks the Generalitat de Catalunya for Next Generation co-fund (PRTR-C17.I1) and the prize ICREA Academia 2023.Peer reviewedRoyal Society of Chemistry (UK)Agencia Estatal de Investigación (España)Ministerio de Ciencia, Innovación y Universidades (España)Gobierno de AragónDepartment of Energy (US)ALBA SynchrotronMinistry of Science and Higher Education of the Russian FederationGeneralitat de CatalunyaConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202420242024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/371016reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI//TED2021-129214B-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-137764OB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-118329RB-I00The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1039/D4SC01365Dhttps://doi.org/10.1039/D4SC01365DSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3710162026-05-22T06:33:51Z
dc.title.none.fl_str_mv Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure
title Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure
spellingShingle Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure
Risa, Arnau
title_short Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure
title_full Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure
title_fullStr Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure
title_full_unstemmed Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure
title_sort Engineered π⋯π interactions favour supramolecular dimers X@[FeL3]2 (X = Cl, Br, I): solid state and solution structure
dc.creator.none.fl_str_mv Risa, Arnau
Barrios, Leoní A.
Diego, Rosa
Roubeau, Olivier
Aleshin, Dmitry Y.
Nelyubina, Yulia
Novikov, Valentin
Teat, Simon J.
Ribas-Ariño, Jordi
Aromí, Guillem
author Risa, Arnau
author_facet Risa, Arnau
Barrios, Leoní A.
Diego, Rosa
Roubeau, Olivier
Aleshin, Dmitry Y.
Nelyubina, Yulia
Novikov, Valentin
Teat, Simon J.
Ribas-Ariño, Jordi
Aromí, Guillem
author_role author
author2 Barrios, Leoní A.
Diego, Rosa
Roubeau, Olivier
Aleshin, Dmitry Y.
Nelyubina, Yulia
Novikov, Valentin
Teat, Simon J.
Ribas-Ariño, Jordi
Aromí, Guillem
author2_role author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Agencia Estatal de Investigación (España)
Ministerio de Ciencia, Innovación y Universidades (España)
Gobierno de Aragón
Department of Energy (US)
ALBA Synchrotron
Ministry of Science and Higher Education of the Russian Federation
Generalitat de Catalunya
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Ditopic bis-pyrazolylpyridine ligands usually react with divalent metal ions (M2+) to produce dinuclear triple-stranded helicates [M2L3]4+ or, via π⋯π interactions, dimers of monoatomic complexes ([ML3]2)4+. The introduction of an additional benzene ring at each end of ligand L increases the number of aromatic contacts within the supramolecular aggregate by 40%, driving the self-recognition process in an irreversible manner. Consequently, the mixing of new bis-pyrazolylquinoline L2 with FeX2 salts leads to crystallization of the tripartite high-spin assemblies (X@[Fe(L2)3]2)3+ (X = Cl, Br or I). The aggregates exhibit exceptional stability, as confirmed by a combination of paramagnetic 1H NMR techniques, demonstrating their persistence in solution. Our investigations further reveal that the guests Br− and I− are retained inside the associate in solution but Cl− is immediately released, resulting in the formation of the empty supramolecular dimer ([Fe(L2)3]2)4+.
publishDate 2024
dc.date.none.fl_str_mv 2024
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/371016
url http://hdl.handle.net/10261/371016
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI//TED2021-129214B-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-137764OB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-118329RB-I00
The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1039/D4SC01365D
https://doi.org/10.1039/D4SC01365D
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry (UK)
publisher.none.fl_str_mv Royal Society of Chemistry (UK)
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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