Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions

Magnetism is typically associated with d- or f-block elements, but can also appear in organic molecules with unpaired π-electrons. This has considerably boosted the interest in such organic materials with large potential for spintronics and quantum applications. While several materials showing eithe...

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Autores: Sun, Qiang, Mateo, Luis M., Robles, Roberto, Ruffieux, Pascal, Bottari, Giovanni, Lorente, Nicolás
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2022
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/287362
Acceso en línea:http://hdl.handle.net/10261/287362
Access Level:acceso abierto
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spelling Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ionsSun, QiangMateo, Luis M.Robles, RobertoRuffieux, PascalBottari, GiovanniLorente, NicolásMagnetism is typically associated with d- or f-block elements, but can also appear in organic molecules with unpaired π-electrons. This has considerably boosted the interest in such organic materials with large potential for spintronics and quantum applications. While several materials showing either d/f or π-electron magnetism have been synthesized, the combination of both features within the same structure has only scarcely been reported. Open-shell porphyrins (Pors) incorporating d-block transition metal ions represent an ideal platform for the realization of such architectures. Herein, the preparation of a series of open-shell, π-extended Pors that contain magnetically active metal ions (i.e., CuII, CoII, and FeII) through a combination of in-solution and on-surface synthesis is reported. A detailed study of the magnetic interplay between π- and d-electrons in these metalloPors has been performed by scanning probe methods and density functional theory calculations. For the Cu and FePors, ferromagnetically coupled π-electrons are determined to be delocalized over the Por edges. For the CoPor, the authors find a Kondo resonance resulting from the singly occupied CoII dz2 orbital to dominate the magnetic fingerprint. The Fe derivative exhibits the highest magnetization of 3.67 μB (S≈2) and an exchange coupling of 16 meV between the π-electrons and the Fe d-states.This work was supported by the Swiss National Science Foundation under Grant No. 200020_182015, the European Union's Horizon 2020 research and innovation programme under grant agreement number 785219 (Graphene Flagship Core 2), MINECO, CTQ2017-85393-P (Phthalophoto, TT), and PID2020-116490GBI00 (Porphyrinoids, TT, GB). IMDEA Nanociencia also acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV-2016-0686). R.R. and N.L. are grateful for funding from the EU-FET Open H2020 Mechanics with Molecules project (grant 766864) and from Spanish State Research Agency grant RTI2018-097895-B-C44 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”. Q. S. acknowledges the financial support from the National Natural Science Foundation of China (No. 22072086).Peer reviewedWiley-VCHSwiss National Science FoundationEuropean CommissionMinisterio de Ciencia, Innovación y Universidades (España)Agencia Estatal de Investigación (España)Ministerio de Economía y Competitividad (España)National Natural Science Foundation of ChinaConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202320232022info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/287362reponame: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/EC/H2020/785219info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-85393-Pinfo:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-116490GB-I00info:eu-repo/grantAgreement/MINECO//SEV-2016-0686info:eu-repo/grantAgreement/EC/H2020/766864info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-097895-B-C44The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1002/advs.202105906https://doi.org/10.1002/advs.202105906Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/2873622026-05-22T06:33:51Z
dc.title.none.fl_str_mv Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions
title Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions
spellingShingle Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions
Sun, Qiang
title_short Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions
title_full Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions
title_fullStr Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions
title_full_unstemmed Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions
title_sort Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ions
dc.creator.none.fl_str_mv Sun, Qiang
Mateo, Luis M.
Robles, Roberto
Ruffieux, Pascal
Bottari, Giovanni
Lorente, Nicolás
author Sun, Qiang
author_facet Sun, Qiang
Mateo, Luis M.
Robles, Roberto
Ruffieux, Pascal
Bottari, Giovanni
Lorente, Nicolás
author_role author
author2 Mateo, Luis M.
Robles, Roberto
Ruffieux, Pascal
Bottari, Giovanni
Lorente, Nicolás
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Swiss National Science Foundation
European Commission
Ministerio de Ciencia, Innovación y Universidades (España)
Agencia Estatal de Investigación (España)
Ministerio de Economía y Competitividad (España)
National Natural Science Foundation of China
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description Magnetism is typically associated with d- or f-block elements, but can also appear in organic molecules with unpaired π-electrons. This has considerably boosted the interest in such organic materials with large potential for spintronics and quantum applications. While several materials showing either d/f or π-electron magnetism have been synthesized, the combination of both features within the same structure has only scarcely been reported. Open-shell porphyrins (Pors) incorporating d-block transition metal ions represent an ideal platform for the realization of such architectures. Herein, the preparation of a series of open-shell, π-extended Pors that contain magnetically active metal ions (i.e., CuII, CoII, and FeII) through a combination of in-solution and on-surface synthesis is reported. A detailed study of the magnetic interplay between π- and d-electrons in these metalloPors has been performed by scanning probe methods and density functional theory calculations. For the Cu and FePors, ferromagnetically coupled π-electrons are determined to be delocalized over the Por edges. For the CoPor, the authors find a Kondo resonance resulting from the singly occupied CoII dz2 orbital to dominate the magnetic fingerprint. The Fe derivative exhibits the highest magnetization of 3.67 μB (S≈2) and an exchange coupling of 16 meV between the π-electrons and the Fe d-states.
publishDate 2022
dc.date.none.fl_str_mv 2022
2023
2023
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/10261/287362
url http://hdl.handle.net/10261/287362
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/EC/H2020/785219
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-85393-P
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-116490GB-I00
info:eu-repo/grantAgreement/MINECO//SEV-2016-0686
info:eu-repo/grantAgreement/EC/H2020/766864
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-097895-B-C44
The underlying dataset has been published as supplementary material of the article in the publisher platform at DOI 10.1002/advs.202105906
https://doi.org/10.1002/advs.202105906
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 Wiley-VCH
publisher.none.fl_str_mv Wiley-VCH
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
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