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 De Doni, Luis Manuel, Robles, Roberto, Ruffieux, Pascal, Bottari, Giovanni, Torres Cebada, Tomás, Fasel, Roman, Lorente, Nicolás
Formato: artículo
Fecha de publicación:2022
País:España
Recursos:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/706355
Acesso em linha:http://hdl.handle.net/10486/706355
https://dx.doi.org/10.1002/advs.202105906
Access Level:acceso abierto
Palavra-chave:Electrons
Iron Compounds
Magnetism
Metal Ions
Shells (Structures)
Transition Metals
Química
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spelling Magnetic interplay between π-electrons of open-shell porphyrins and d-electrons of their central transition metal ionsSun, QiangMateo De Doni, Luis ManuelRobles, RobertoRuffieux, PascalBottari, GiovanniTorres Cebada, TomásFasel, RomanLorente, NicolásElectronsIron CompoundsMagnetismMetal IonsShells (Structures)Transition MetalsQuímicaMagnetism 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-statesWiley Open AccessDepartamento de Química OrgánicaFacultad de Ciencias20222022-03-18research articlehttp://purl.org/coar/resource_type/c_2df8fbb1VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/706355https://dx.doi.org/10.1002/advs.202105906reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengEuropean Commission http://dx.doi.org/10.13039/501100000780 Horizon 2020 Framework Programme 785219European Commission http://dx.doi.org/10.13039/501100000780 Horizon 2020 Framework Programme 766864open accesshttp://purl.org/coar/access_right/c_abf2info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/7063552026-06-23T12:46:27Z
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
Electrons
Iron Compounds
Magnetism
Metal Ions
Shells (Structures)
Transition Metals
Química
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 De Doni, Luis Manuel
Robles, Roberto
Ruffieux, Pascal
Bottari, Giovanni
Torres Cebada, Tomás
Fasel, Roman
Lorente, Nicolás
author Sun, Qiang
author_facet Sun, Qiang
Mateo De Doni, Luis Manuel
Robles, Roberto
Ruffieux, Pascal
Bottari, Giovanni
Torres Cebada, Tomás
Fasel, Roman
Lorente, Nicolás
author_role author
author2 Mateo De Doni, Luis Manuel
Robles, Roberto
Ruffieux, Pascal
Bottari, Giovanni
Torres Cebada, Tomás
Fasel, Roman
Lorente, Nicolás
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Departamento de Química Orgánica
Facultad de Ciencias
dc.subject.none.fl_str_mv Electrons
Iron Compounds
Magnetism
Metal Ions
Shells (Structures)
Transition Metals
Química
topic Electrons
Iron Compounds
Magnetism
Metal Ions
Shells (Structures)
Transition Metals
Química
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
2022-03-18
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10486/706355
https://dx.doi.org/10.1002/advs.202105906
url http://hdl.handle.net/10486/706355
https://dx.doi.org/10.1002/advs.202105906
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv European Commission http://dx.doi.org/10.13039/501100000780 Horizon 2020 Framework Programme 785219



European Commission http://dx.doi.org/10.13039/501100000780 Horizon 2020 Framework Programme 766864
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley Open Access
publisher.none.fl_str_mv Wiley Open Access
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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