Tuning the spin interaction in nonplanar organic diradicals through mechanical manipulation

Open-shell polycyclic aromatic hydrocarbons (PAHs) represent promising building blocks for carbon-based functional magnetic materials. Their magnetic properties stem from the presence of unpaired electrons localized in radical states of π character. Consequently, these materials are inclined to exhi...

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Autores: Vegliante, Alessio, Fernández, Saleta, Ortiz, Ricardo, Vilas-Varela, Manuel, Baum, Thomas Y., Friedrich, Niklas, Romero Lara, Francisco, Aguirre Baños, Andrea, Vaxevani, Katerina, Wang, Dongfei, García-Fernández, Carlos, Zant, Herre S. J. van der, Frederiksen, Thomas, Peña, Diego, Pascual, José I.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2024
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/373933
Acceso en línea:http://hdl.handle.net/10261/373933
Access Level:acceso abierto
Palabra clave:Organic diradicals
Carbon magnetism
n-surface synthesis
Exchange coupling
Scanning tunneling microscopy
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dc.title.none.fl_str_mv Tuning the spin interaction in nonplanar organic diradicals through mechanical manipulation
title Tuning the spin interaction in nonplanar organic diradicals through mechanical manipulation
spellingShingle Tuning the spin interaction in nonplanar organic diradicals through mechanical manipulation
Vegliante, Alessio
Organic diradicals
Carbon magnetism
n-surface synthesis
Exchange coupling
Scanning tunneling microscopy
title_short Tuning the spin interaction in nonplanar organic diradicals through mechanical manipulation
title_full Tuning the spin interaction in nonplanar organic diradicals through mechanical manipulation
title_fullStr Tuning the spin interaction in nonplanar organic diradicals through mechanical manipulation
title_full_unstemmed Tuning the spin interaction in nonplanar organic diradicals through mechanical manipulation
title_sort Tuning the spin interaction in nonplanar organic diradicals through mechanical manipulation
dc.creator.none.fl_str_mv Vegliante, Alessio
Fernández, Saleta
Ortiz, Ricardo
Vilas-Varela, Manuel
Baum, Thomas Y.
Friedrich, Niklas
Romero Lara, Francisco
Aguirre Baños, Andrea
Vaxevani, Katerina
Wang, Dongfei
García-Fernández, Carlos
Zant, Herre S. J. van der
Frederiksen, Thomas
Peña, Diego
Pascual, José I.
author Vegliante, Alessio
author_facet Vegliante, Alessio
Fernández, Saleta
Ortiz, Ricardo
Vilas-Varela, Manuel
Baum, Thomas Y.
Friedrich, Niklas
Romero Lara, Francisco
Aguirre Baños, Andrea
Vaxevani, Katerina
Wang, Dongfei
García-Fernández, Carlos
Zant, Herre S. J. van der
Frederiksen, Thomas
Peña, Diego
Pascual, José I.
author_role author
author2 Fernández, Saleta
Ortiz, Ricardo
Vilas-Varela, Manuel
Baum, Thomas Y.
Friedrich, Niklas
Romero Lara, Francisco
Aguirre Baños, Andrea
Vaxevani, Katerina
Wang, Dongfei
García-Fernández, Carlos
Zant, Herre S. J. van der
Frederiksen, Thomas
Peña, Diego
Pascual, José I.
author2_role author
author
author
author
author
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)
European Commission
European Research Council
Xunta de Galicia
Ministerio de Educación y Formación Profesional (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Organic diradicals
Carbon magnetism
n-surface synthesis
Exchange coupling
Scanning tunneling microscopy
topic Organic diradicals
Carbon magnetism
n-surface synthesis
Exchange coupling
Scanning tunneling microscopy
description Open-shell polycyclic aromatic hydrocarbons (PAHs) represent promising building blocks for carbon-based functional magnetic materials. Their magnetic properties stem from the presence of unpaired electrons localized in radical states of π character. Consequently, these materials are inclined to exhibit spin delocalization, form extended collective states, and respond to the flexibility of the molecular backbones. However, they are also highly reactive, requiring structural strategies to protect the radical states from reacting with the environment. Here, we demonstrate that the open-shell ground state of the diradical 2-OS survives on a Au(111) substrate as a global singlet formed by two unpaired electrons with antiparallel spins coupled through a conformational-dependent interaction. The 2-OS molecule is a “protected” derivative of the Chichibabin’s diradical, featuring a nonplanar geometry that destabilizes the closed-shell quinoidal structure. Using scanning tunneling microscopy (STM), we localized the two interacting spins at the molecular edges, and detected an excited triplet state a few millielectronvolts above the singlet ground state. Mean-field Hubbard simulations reveal that the exchange coupling between the two spins strongly depends on the torsional angles between the different molecular moieties, suggesting the possibility of influencing the molecule’s magnetic state through structural changes. This was demonstrated here using the STM tip to manipulate the molecular conformation, while simultaneously detecting changes in the spin excitation spectrum. Our work suggests the potential of these PAHs as all-carbon spin-crossover materials.
publishDate 2024
dc.date.none.fl_str_mv 2024
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
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dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/373933
url http://hdl.handle.net/10261/373933
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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Vegliante, Alessio; Fernández, Saleta; Ortiz, Ricardo; Vilas-Varela, Manuel; Baum, Thomas Y.; Friedrich, Niklas; Romero Lara, Francisco; Aguirre Baños, Andrea; Vaxevani, Katerina; Wang, Dongfei; García-Fernández, Carlos; Zant, Herre S. J. van der; Frederiksen, Thomas; Peña, Diego; Pascual, José I.; 2024; Supplementary Information: Tuning the spin interaction in nonplanar organic diradicals through mechanical manipulation [Dataset]; American Chemical Society; https://doi.org/10.1021/acsnano.4c01963
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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
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instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
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spelling Tuning the spin interaction in nonplanar organic diradicals through mechanical manipulationVegliante, AlessioFernández, SaletaOrtiz, RicardoVilas-Varela, ManuelBaum, Thomas Y.Friedrich, NiklasRomero Lara, FranciscoAguirre Baños, AndreaVaxevani, KaterinaWang, DongfeiGarcía-Fernández, CarlosZant, Herre S. J. van derFrederiksen, ThomasPeña, DiegoPascual, José I.Organic diradicalsCarbon magnetismn-surface synthesisExchange couplingScanning tunneling microscopyOpen-shell polycyclic aromatic hydrocarbons (PAHs) represent promising building blocks for carbon-based functional magnetic materials. Their magnetic properties stem from the presence of unpaired electrons localized in radical states of π character. Consequently, these materials are inclined to exhibit spin delocalization, form extended collective states, and respond to the flexibility of the molecular backbones. However, they are also highly reactive, requiring structural strategies to protect the radical states from reacting with the environment. Here, we demonstrate that the open-shell ground state of the diradical 2-OS survives on a Au(111) substrate as a global singlet formed by two unpaired electrons with antiparallel spins coupled through a conformational-dependent interaction. The 2-OS molecule is a “protected” derivative of the Chichibabin’s diradical, featuring a nonplanar geometry that destabilizes the closed-shell quinoidal structure. Using scanning tunneling microscopy (STM), we localized the two interacting spins at the molecular edges, and detected an excited triplet state a few millielectronvolts above the singlet ground state. Mean-field Hubbard simulations reveal that the exchange coupling between the two spins strongly depends on the torsional angles between the different molecular moieties, suggesting the possibility of influencing the molecule’s magnetic state through structural changes. This was demonstrated here using the STM tip to manipulate the molecular conformation, while simultaneously detecting changes in the spin excitation spectrum. Our work suggests the potential of these PAHs as all-carbon spin-crossover materials.The authors gratefully acknowledge financial support from the Spanish MCIN/AEI/10.13039/501100011033 and the European Regional Development Fund (ERDF) through grants PID2022-140845OB-C61, PID2022-140845OB-C62, PID2020-115406GB-I00, and the Maria de Maeztu Units of Excellence Program CEX2020-001038-M, from the European Union (EU) through the FET-Open project SPRING (863098), the ERC Synergy Grant MolDAM (951519), the ERC-AdG CONSPIRA (101097693), and from the Xunta de Galicia (Centro singular de investigación de Galicia accreditation 2019-2022, ED431G 2019/03 and Oportunius Program). F.R.-L. acknowledges funding by the Spanish Ministerio de Educación y Formación Profesional through the PhD scholarship No. FPU20/03305.With funding from the Spanish government through the "Unit of Excellence Maria de Maeztu" accreditation (CEX2020-001038-M).Peer reviewedAmerican Chemical SocietyAgencia Estatal de Investigación (España)Ministerio de Ciencia, Innovación y Universidades (España)European CommissionEuropean Research CouncilXunta de GaliciaMinisterio de Educación y Formación Profesional (España)Consejo 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/10261/373933reponame: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##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-140845OB-C61info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-140845OB-C62info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-115406GB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CEX2020-001038-Minfo:eu-repo/grantAgreement/EC/H2020/863098info:eu-repo/grantAgreement/EC/H2020/951519info:eu-repo/grantAgreement/EC/HE/101097693Vegliante, Alessio; Fernández, Saleta; Ortiz, Ricardo; Vilas-Varela, Manuel; Baum, Thomas Y.; Friedrich, Niklas; Romero Lara, Francisco; Aguirre Baños, Andrea; Vaxevani, Katerina; Wang, Dongfei; García-Fernández, Carlos; Zant, Herre S. J. van der; Frederiksen, Thomas; Peña, Diego; Pascual, José I.; 2024; Supplementary Information: Tuning the spin interaction in nonplanar organic diradicals through mechanical manipulation [Dataset]; American Chemical Society; https://doi.org/10.1021/acsnano.4c01963https://doi.org/10.1021/acsnano.4c01963Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3739332026-05-22T06:33:51Z
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