BINOL-Containing Chiral Porous Polymers as Platforms for Enantiorecognition

The enantioselective discrimination of racemic compounds can be achieved through the design and preparation of a new family of chiral conjugated BINOL-porous polymers (CBPPs) from enantiopure (R)- or (S)-BINOL derivatives and 1,3,5-tris(4-phenylboronic acid)benzene or 1,3,5-tris(4-ethynylphenyl)benz...

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Authors: Valverde-Gónzález, Antonio, Borrallo-Aniceto, M. Carmen, Pintado-Sierra, Mercedes, Sánchez, Félix, Arnanz, Avelina, Boronat, Mercedes, Iglesias, Marta
Format: article
Status:Versión aceptada para publicación
Publication Date:2022
Country:España
Institution:Consejo Superior de Investigaciones Científicas (CSIC)
Repository:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/290850
Online Access:http://hdl.handle.net/10261/290850
Access Level:Open access
Keyword:chiral porous polymers, BINOL building blocks, enantioselective recognition, fluorescence, terpenes
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spelling BINOL-Containing Chiral Porous Polymers as Platforms for EnantiorecognitionValverde-Gónzález, AntonioBorrallo-Aniceto, M. CarmenPintado-Sierra, MercedesSánchez, FélixArnanz, AvelinaBoronat, MercedesIglesias, Martachiral porous polymers, BINOL building blocks, enantioselective recognition, fluorescence, terpenesThe enantioselective discrimination of racemic compounds can be achieved through the design and preparation of a new family of chiral conjugated BINOL-porous polymers (CBPPs) from enantiopure (R)- or (S)-BINOL derivatives and 1,3,5-tris(4-phenylboronic acid)benzene or 1,3,5-tris(4-ethynylphenyl)benzene, 1,3,5-triethynyl-2,4,6-trifluorobenzene, and tetra(4-ethynylphenyl)methane as comonomers following Suzuki-Miyaura and Sonogashira-Hagihara carbon-carbon coupling approaches. The obtained CBPPs show high thermal stability, a good specific surface area, and a robust framework and can be applied successfully in the fluorescence recognition of enantiomers of terpenes (limonene and α-pinene) and 1-phenylethylamine. Fluorescence titration of CBPPs-OH in acetonitrile shows that all Sonogashira hosts exhibit a preference for the (R)-enantiomer over the (S)-enantiomer of 1-phenylethylamine, the selectivity being much higher than that of the corresponding BINOL-based soluble system used as a reference. However, the Suzuki host reveals a preference toward (S)-phenylethylamine. Regarding the sensing of terpenes, only Sonogashira hosts show enantiodifferentiation with an almost total preference for the (S)-enantiomer of limonene and α-pinene. Based on the computational simulations and the experimental data, with 1-phenylethylamine as the analyte, chiral recognition is due to the distinctive binding affinities resulting from N···H-O hydrogen bonds and the π-πinteraction between the host and the guest. However, for limonene, the geometry of the adsorption complex is mostly governed by the interaction between the hydroxyl group of the BINOL unit and the C═C bond of the iso-propenyl fragment. The synthetic strategy used to prepare CBPPs opens many possibilities to place chiral centers such as BINOL in porous polymers for different chiral applications such as enantiomer recognition.Authors acknowledge Grants PID2020-112590GB-C22 and PID2020-112590GB-C21 funded by MCIN/AEI/10.13039/501100011033. A.V.G. thanks Ministerio de Universidades for FPU17/03463.Peer reviewedAmerican Chemical SocietyMinisterio de Ciencia e Innovación (España)Agencia Estatal de Investigación (España)Ministerio de Universidades (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2023202320222023info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/290850reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-112590GB-C22info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-112590GB-C21http://dx.doi.org/10.1021/acsami.2c18074Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2908502026-05-22T06:33:51Z
dc.title.none.fl_str_mv BINOL-Containing Chiral Porous Polymers as Platforms for Enantiorecognition
title BINOL-Containing Chiral Porous Polymers as Platforms for Enantiorecognition
spellingShingle BINOL-Containing Chiral Porous Polymers as Platforms for Enantiorecognition
Valverde-Gónzález, Antonio
chiral porous polymers, BINOL building blocks, enantioselective recognition, fluorescence, terpenes
title_short BINOL-Containing Chiral Porous Polymers as Platforms for Enantiorecognition
title_full BINOL-Containing Chiral Porous Polymers as Platforms for Enantiorecognition
title_fullStr BINOL-Containing Chiral Porous Polymers as Platforms for Enantiorecognition
title_full_unstemmed BINOL-Containing Chiral Porous Polymers as Platforms for Enantiorecognition
title_sort BINOL-Containing Chiral Porous Polymers as Platforms for Enantiorecognition
dc.creator.none.fl_str_mv Valverde-Gónzález, Antonio
Borrallo-Aniceto, M. Carmen
Pintado-Sierra, Mercedes
Sánchez, Félix
Arnanz, Avelina
Boronat, Mercedes
Iglesias, Marta
author Valverde-Gónzález, Antonio
author_facet Valverde-Gónzález, Antonio
Borrallo-Aniceto, M. Carmen
Pintado-Sierra, Mercedes
Sánchez, Félix
Arnanz, Avelina
Boronat, Mercedes
Iglesias, Marta
author_role author
author2 Borrallo-Aniceto, M. Carmen
Pintado-Sierra, Mercedes
Sánchez, Félix
Arnanz, Avelina
Boronat, Mercedes
Iglesias, Marta
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
Agencia Estatal de Investigación (España)
Ministerio de Universidades (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv chiral porous polymers, BINOL building blocks, enantioselective recognition, fluorescence, terpenes
topic chiral porous polymers, BINOL building blocks, enantioselective recognition, fluorescence, terpenes
description The enantioselective discrimination of racemic compounds can be achieved through the design and preparation of a new family of chiral conjugated BINOL-porous polymers (CBPPs) from enantiopure (R)- or (S)-BINOL derivatives and 1,3,5-tris(4-phenylboronic acid)benzene or 1,3,5-tris(4-ethynylphenyl)benzene, 1,3,5-triethynyl-2,4,6-trifluorobenzene, and tetra(4-ethynylphenyl)methane as comonomers following Suzuki-Miyaura and Sonogashira-Hagihara carbon-carbon coupling approaches. The obtained CBPPs show high thermal stability, a good specific surface area, and a robust framework and can be applied successfully in the fluorescence recognition of enantiomers of terpenes (limonene and α-pinene) and 1-phenylethylamine. Fluorescence titration of CBPPs-OH in acetonitrile shows that all Sonogashira hosts exhibit a preference for the (R)-enantiomer over the (S)-enantiomer of 1-phenylethylamine, the selectivity being much higher than that of the corresponding BINOL-based soluble system used as a reference. However, the Suzuki host reveals a preference toward (S)-phenylethylamine. Regarding the sensing of terpenes, only Sonogashira hosts show enantiodifferentiation with an almost total preference for the (S)-enantiomer of limonene and α-pinene. Based on the computational simulations and the experimental data, with 1-phenylethylamine as the analyte, chiral recognition is due to the distinctive binding affinities resulting from N···H-O hydrogen bonds and the π-πinteraction between the host and the guest. However, for limonene, the geometry of the adsorption complex is mostly governed by the interaction between the hydroxyl group of the BINOL unit and the C═C bond of the iso-propenyl fragment. The synthetic strategy used to prepare CBPPs opens many possibilities to place chiral centers such as BINOL in porous polymers for different chiral applications such as enantiomer recognition.
publishDate 2022
dc.date.none.fl_str_mv 2022
2023
2023
2023
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/10261/290850
url http://hdl.handle.net/10261/290850
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#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-112590GB-C22
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-112590GB-C21
http://dx.doi.org/10.1021/acsami.2c18074
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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 15,198674

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