An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter

A new persistent organic free radical has been synthetized with Br atoms occupying the ortho‐ and para‐positions of a trityl core. After the isolation of its two propeller‐like atropisomers, Plus (P) and minus (M), their absolute configurations were assigned by a combination of theoretical and exper...

Descripción completa

Detalles Bibliográficos
Autores: Mayorga-Burrezo, Paula, Jiménez, Vicente G., Blasi, Davide, Parella, Teodor, Ratera, Immaculada, Campaña, Araceli G., Veciana, Jaume
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2020
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/233350
Acceso en línea:http://hdl.handle.net/10261/233350
Access Level:acceso abierto
Palabra clave:Bromine substituents
Crcularly polarized luminescence
Racemization barrier
Radicals
Trityl radical
id ES_6128f10c812fd5dd80da621768efe72c
oai_identifier_str oai:digital.csic.es:10261/233350
network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter
title An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter
spellingShingle An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter
Mayorga-Burrezo, Paula
Bromine substituents
Crcularly polarized luminescence
Racemization barrier
Radicals
Trityl radical
title_short An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter
title_full An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter
title_fullStr An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter
title_full_unstemmed An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter
title_sort An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic Emitter
dc.creator.none.fl_str_mv Mayorga-Burrezo, Paula
Jiménez, Vicente G.
Blasi, Davide
Parella, Teodor
Ratera, Immaculada
Campaña, Araceli G.
Veciana, Jaume
author Mayorga-Burrezo, Paula
author_facet Mayorga-Burrezo, Paula
Jiménez, Vicente G.
Blasi, Davide
Parella, Teodor
Ratera, Immaculada
Campaña, Araceli G.
Veciana, Jaume
author_role author
author2 Jiménez, Vicente G.
Blasi, Davide
Parella, Teodor
Ratera, Immaculada
Campaña, Araceli G.
Veciana, Jaume
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Dirección General de Investigación Científica y Técnica, DGICT (España)
Generalitat de Catalunya
Ministerio de Economía y Competitividad (España)
European Research Council
Centro de Investigación Biomédica en Red Bioingeniería, Biomateriales y Nanomedicina (España)
Instituto de Salud Carlos III
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Bromine substituents
Crcularly polarized luminescence
Racemization barrier
Radicals
Trityl radical
topic Bromine substituents
Crcularly polarized luminescence
Racemization barrier
Radicals
Trityl radical
description A new persistent organic free radical has been synthetized with Br atoms occupying the ortho‐ and para‐positions of a trityl core. After the isolation of its two propeller‐like atropisomers, Plus (P) and minus (M), their absolute configurations were assigned by a combination of theoretical and experimental data. Remarkably, no hints of racemization were observed up to 60 °C for more than two hours, due to the higher steric hindrance imposed by the bulky Br atoms. Therefore, when compared to its chlorinated homologue (t1/2=18 s at 60 °C), an outstanding stability against racemization was achieved. A circularly polarized luminescence (CPL) response of both enantiomers was detected. This free radical shows a satisfactory luminescent dissymmetry factor (|glum(592 nm)|≈0.7×10−3) despite its pure organic nature and low luminescence quantum yield (LQY). Improved organic magnetic CPL emitters derived from the reported structure can be envisaged thanks to the wide possibilities that Br atoms at para‐positions offer for further functionalization.
publishDate 2020
dc.date.none.fl_str_mv 2020
2021
2021
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/10261/233350
url http://hdl.handle.net/10261/233350
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#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2016‐80826‐R
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016‐80030‐R
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018‐095808‐B‐I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018‐101181‐B‐I00
info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SEV-2015-0496
info:eu-repo/grantAgreement/EC/H2020/677023
http://dx.doi.org/10.1002/chem.202000098
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
_version_ 1869409383350272000
spelling An Enantiopure Propeller‐Like Trityl‐Brominated Radical: Bringing Together a High Racemization Barrier and an Efficient Circularly Polarized Luminescent Magnetic EmitterMayorga-Burrezo, PaulaJiménez, Vicente G.Blasi, DavideParella, TeodorRatera, ImmaculadaCampaña, Araceli G.Veciana, JaumeBromine substituentsCrcularly polarized luminescenceRacemization barrierRadicalsTrityl radicalA new persistent organic free radical has been synthetized with Br atoms occupying the ortho‐ and para‐positions of a trityl core. After the isolation of its two propeller‐like atropisomers, Plus (P) and minus (M), their absolute configurations were assigned by a combination of theoretical and experimental data. Remarkably, no hints of racemization were observed up to 60 °C for more than two hours, due to the higher steric hindrance imposed by the bulky Br atoms. Therefore, when compared to its chlorinated homologue (t1/2=18 s at 60 °C), an outstanding stability against racemization was achieved. A circularly polarized luminescence (CPL) response of both enantiomers was detected. This free radical shows a satisfactory luminescent dissymmetry factor (|glum(592 nm)|≈0.7×10−3) despite its pure organic nature and low luminescence quantum yield (LQY). Improved organic magnetic CPL emitters derived from the reported structure can be envisaged thanks to the wide possibilities that Br atoms at para‐positions offer for further functionalization.The authors are grateful for the financial support received from: MOTHER (MAT2016‐80826‐R) and FANCY (CTQ2016‐80030‐R) projects, granted by the DGI (Spain), GenCat (2017‐SGR‐918) financed by DGR (Catalunya) and the Spanish Ministry of Economy and Competitiveness (PGC2018‐095808‐B‐I00 and PGC2018‐101181‐B‐I00 projects) and through the „Severo Ochoa“ Programme for Centres of Excellence in R&D (SEV‐2015‐0496) and through the „Proyecto Interdisciplinar de Frontera“, FIP‐2018 HECTIC‐PTM. We acknowledge the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (ERC‐2015‐STG‐677023). This study has been also supported by the Networking Research Center on Bioengineering, Biomaterials and Nanomedicine (CIBER‐BBN), an initiative funded by the VI National R&D&I Plan 2008–2011, Iniciativa Ingenio 2010, Consolider Program, CIBER Actions and financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund. P.M.B. gratefully acknowledges financial support from the Juan de la Cierva‐Formación 2015 programme (FJCI‐2015–23577) supported by MINECO and, together with J.V, A.G.C. is grateful for a RyC‐2013–12943 contract from MINECO. We also thank the Servei de Ressonància Magnètica Nuclear, Universitat Autònoma de Barcelona, for allocating instrument time to this project.Peer reviewedWiley-VCHDirección General de Investigación Científica y Técnica, DGICT (España)Generalitat de CatalunyaMinisterio de Economía y Competitividad (España)European Research CouncilCentro de Investigación Biomédica en Red Bioingeniería, Biomateriales y Nanomedicina (España)Instituto de Salud Carlos IIIConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202120212020info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Postprintinfo:eu-repo/semantics/acceptedVersionhttp://hdl.handle.net/10261/233350reponame: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##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/MAT2016‐80826‐Rinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016‐80030‐Rinfo:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018‐095808‐B‐I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018‐101181‐B‐I00info:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/SEV-2015-0496info:eu-repo/grantAgreement/EC/H2020/677023http://dx.doi.org/10.1002/chem.202000098Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2333502026-05-22T06:33:51Z
score 15,811543

Similares en LA Referencia