On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales Topologies

The incorporation of non-benzenoid motifs in graphene nanostructures significantly impacts their properties, making them attractive for applications in carbon-based electronics. However, understanding how specific nonbenzenoid structures influence their properties remains limited, and further invest...

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Autores: Biswas, Kalyan, Chen, Qifan, Obermann, Sebastian, Ma, Ji, Melidonie, Jason, Lauwaet, Koen, Jelínek, Pavel, Feng, Xinliang, Soler Polo, Diego Manuel, Barragán, Ana, Sánchez Grande, Ana, Gallego, José M., Écija, David, Urgel, José I., Miranda Soriano, Rodolfo
Tipo de documento: artigo
Data de publicação:2024
País:España
Recursos:Universidad Autónoma de Madrid
Repositório:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglês
OAI Identifier:oai:repositorio.uam.es:10486/715719
Acesso em linha:http://hdl.handle.net/10486/715719
https://dx.doi.org/10.1002/ange.202318185
Access Level:Acceso aberto
Palavra-chave:Nanographenes
azulene and Stone-Wales defects
scanning tunnelling microscopy
open-shell species
oxidative ring-closure
Física
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spelling On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales TopologiesBiswas, KalyanChen, QifanObermann, SebastianMa, JiMelidonie, JasonLauwaet, KoenJelínek, PavelFeng, XinliangSoler Polo, Diego ManuelBarragán, AnaSánchez Grande, AnaGallego, José M.Écija, DavidUrgel, José I.Miranda Soriano, RodolfoNanographenesazulene and Stone-Wales defectsscanning tunnelling microscopyopen-shell speciesoxidative ring-closureFísicaThe incorporation of non-benzenoid motifs in graphene nanostructures significantly impacts their properties, making them attractive for applications in carbon-based electronics. However, understanding how specific nonbenzenoid structures influence their properties remains limited, and further investigations are needed to fully comprehend their implications. Here, we report an on-surface synthetic strategy toward fabricating non-benzenoid nanographenes containing different combinations of pentagonal and heptagonal rings. Their structure and electronic properties were investigated via scanning tunneling microscopy and spectroscopy, complemented by computational investigations. After thermal activation of the precursor P on the Au(111) surface, we detected two major nanographene products. Nanographene Aa- a embeds two azulene units formed through oxidative ring-closure of methyl substituents, while Aa-s contains one azulene unit and one Stone-Wales defect, formed by the combination of oxidative ring-closure and skeletal ring-rearrangement reactions. Aa-a exhibits an antiferromagnetic ground state with the highest magnetic exchange coupling reported up to date for a non-benzenoid containing nanographene, coexisting with side-products with closed shell configurations resulted from the combination of ring-closure and ring-rearragement reactions (Ba-a, Ba-s, Bs-a and Bs-s). Our results provide insights into the single gold atom assisted synthesis of novel NGs containing nonbenzenoid motifs and their tailored electronic/magnetic propertiesThe authors acknowledge to several funding organizations for their financial support. We thank support from the ‘(MAD2D-CM)-IMDEA-Nanociencia’ project funded by Comunidad de Madrid, by the Recovery, Transformation and Resilience Plan, and by NextGenerationEU from the European Union; the QUIMTRONIC-CM project (Y2018/NMT-4783) by Comunidad de Madrid; and the Ministerio de Ciencia e Innovación for the PID2019-108532GB-I00 project. IMDEA Nanociencia also acknowledges the “Severo Ochoa” Programme for Centers of Excellence in R&D (MINECO, Grant SEV-2016-0686 and CEX2020-001039-S). We acknowledge support from the CzechNanoLab Research Infrastructure supported by MEYS CR (LM2023051) and the GACR project no. 23-05486S. Computational resources were provided by the e-INFRA CZ project (ID: 90254), supported by MEYS CR. In addition, we appreciate financial support by the EU Graphene Flagship (Graphene Core 3, 881603), the Center for Advancing Electronics Dresden (CFAED), H2020-EU.1.2.2.–FET Proactive Grant (LIGHT-CAP, 101017821) and the DFG-SNSF Joint Switzerland-German Research Project (EnhanTopo, No. 429265950). J. I. U. acknowledges the funding from the Marie Skłodowska-Curie grant agreement no. 886314, which is part of the European Union's Horizon 2020 research and innovation programme. Open Access publishing facilitated by Fyzikalni ustav Akademie ved Ceske republiky, as part of the Wiley - CzechELib agreementWiley VCH GmbHDepartamento de Física de la Materia CondensadaFacultad de Ciencias20242024-02-22research articlehttp://purl.org/coar/resource_type/c_2df8fbb1VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/715719https://dx.doi.org/10.1002/ange.202318185reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/7157192026-06-23T12:46:27Z
dc.title.none.fl_str_mv On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales Topologies
title On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales Topologies
spellingShingle On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales Topologies
Biswas, Kalyan
Nanographenes
azulene and Stone-Wales defects
scanning tunnelling microscopy
open-shell species
oxidative ring-closure
Física
title_short On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales Topologies
title_full On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales Topologies
title_fullStr On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales Topologies
title_full_unstemmed On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales Topologies
title_sort On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales Topologies
dc.creator.none.fl_str_mv Biswas, Kalyan
Chen, Qifan
Obermann, Sebastian
Ma, Ji
Melidonie, Jason
Lauwaet, Koen
Jelínek, Pavel
Feng, Xinliang
Soler Polo, Diego Manuel
Barragán, Ana
Sánchez Grande, Ana
Gallego, José M.
Écija, David
Urgel, José I.
Miranda Soriano, Rodolfo
author Biswas, Kalyan
author_facet Biswas, Kalyan
Chen, Qifan
Obermann, Sebastian
Ma, Ji
Melidonie, Jason
Lauwaet, Koen
Jelínek, Pavel
Feng, Xinliang
Soler Polo, Diego Manuel
Barragán, Ana
Sánchez Grande, Ana
Gallego, José M.
Écija, David
Urgel, José I.
Miranda Soriano, Rodolfo
author_role author
author2 Chen, Qifan
Obermann, Sebastian
Ma, Ji
Melidonie, Jason
Lauwaet, Koen
Jelínek, Pavel
Feng, Xinliang
Soler Polo, Diego Manuel
Barragán, Ana
Sánchez Grande, Ana
Gallego, José M.
Écija, David
Urgel, José I.
Miranda Soriano, Rodolfo
author2_role author
author
author
author
author
author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Departamento de Física de la Materia Condensada
Facultad de Ciencias
dc.subject.none.fl_str_mv Nanographenes
azulene and Stone-Wales defects
scanning tunnelling microscopy
open-shell species
oxidative ring-closure
Física
topic Nanographenes
azulene and Stone-Wales defects
scanning tunnelling microscopy
open-shell species
oxidative ring-closure
Física
description The incorporation of non-benzenoid motifs in graphene nanostructures significantly impacts their properties, making them attractive for applications in carbon-based electronics. However, understanding how specific nonbenzenoid structures influence their properties remains limited, and further investigations are needed to fully comprehend their implications. Here, we report an on-surface synthetic strategy toward fabricating non-benzenoid nanographenes containing different combinations of pentagonal and heptagonal rings. Their structure and electronic properties were investigated via scanning tunneling microscopy and spectroscopy, complemented by computational investigations. After thermal activation of the precursor P on the Au(111) surface, we detected two major nanographene products. Nanographene Aa- a embeds two azulene units formed through oxidative ring-closure of methyl substituents, while Aa-s contains one azulene unit and one Stone-Wales defect, formed by the combination of oxidative ring-closure and skeletal ring-rearrangement reactions. Aa-a exhibits an antiferromagnetic ground state with the highest magnetic exchange coupling reported up to date for a non-benzenoid containing nanographene, coexisting with side-products with closed shell configurations resulted from the combination of ring-closure and ring-rearragement reactions (Ba-a, Ba-s, Bs-a and Bs-s). Our results provide insights into the single gold atom assisted synthesis of novel NGs containing nonbenzenoid motifs and their tailored electronic/magnetic properties
publishDate 2024
dc.date.none.fl_str_mv 2024
2024-02-22
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/10486/715719
https://dx.doi.org/10.1002/ange.202318185
url http://hdl.handle.net/10486/715719
https://dx.doi.org/10.1002/ange.202318185
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
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
Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley VCH GmbH
publisher.none.fl_str_mv Wiley VCH GmbH
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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