Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers

On‐surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N‐containing pentacene‐based precursor (tetraazapentacene) is ex‐professo synthesized endowed with terminal dibromomethylene (:CBr<jats:...

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Detalhes bibliográficos
Autores: Sánchez-Grande, Ana, Urgel, José, García Benito, Inés, Santos Barahona, José Manuel, Biswas, Kalyan, Lauwaet, Koen, Gallego, José M., Rosen, Johanna, Miranda, Rodolfo, Björk, Jonas, Martín León, Nazario, Écija, David
Formato: artículo
Fecha de publicación:2022
País:España
Recursos:Universidad Complutense de Madrid (UCM)
Repositorio:Docta Complutense
Idioma:español
OAI Identifier:oai:docta.ucm.es:20.500.14352/93405
Acesso em linha:https://hdl.handle.net/20.500.14352/93405
Access Level:acceso abierto
Palavra-chave:547
Química orgánica (Química)
2306 Química Orgánica
id ES_d39c95d1cab1b2759e13402c2f6557b3
oai_identifier_str oai:docta.ucm.es:20.500.14352/93405
network_acronym_str ES
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spelling Surface‐Assisted Synthesis of N‐Containing π‐Conjugated PolymersSánchez-Grande, AnaUrgel, JoséGarcía Benito, InésSantos Barahona, José ManuelBiswas, KalyanLauwaet, KoenGallego, José M.Rosen, JohannaMiranda, RodolfoBjörk, JonasMartín León, NazarioÉcija, David547Química orgánica (Química)2306 Química OrgánicaOn‐surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N‐containing pentacene‐based precursor (tetraazapentacene) is ex‐professo synthesized endowed with terminal dibromomethylene (:CBr<jats:sub>2</jats:sub>) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N‐containing conjugated coordination polymer (P1). Subsequently, P1undergoes ladderization at 200 °C, affording a pyrrolopyrrole‐bridged conjugated polymer (P2). On Au(111) the formation of the intermediate polymer P1 is not observed and, instead, after annealing at 100 °C, the conjugated ladder polymer P2 is obtained, revealing the crucial role of metal adatoms on Ag(111) as compared to Au(111). Finally, on Ag(100) the loss of :CBr2 groups affords the formation of tetraazapentacene monomers, which coexist with polymer P1. Our results contribute to introduce protocols for the synthesis of N‐containing conjugated polymers, illustrating the selective role of the metallic support in the underlying reaction mechanisms.</jats:p>WileyUniversidad Complutense de Madrid20222022-01-0120222022-01-01journal articlehttp://purl.org/coar/resource_type/c_6501info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/20.500.14352/93405reponame:Docta Complutenseinstname:Universidad Complutense de Madrid (UCM)Españolspaopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:docta.ucm.es:20.500.14352/934052026-06-02T12:44:21Z
dc.title.none.fl_str_mv Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers
title Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers
spellingShingle Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers
Sánchez-Grande, Ana
547
Química orgánica (Química)
2306 Química Orgánica
title_short Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers
title_full Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers
title_fullStr Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers
title_full_unstemmed Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers
title_sort Surface‐Assisted Synthesis of N‐Containing π‐Conjugated Polymers
dc.creator.none.fl_str_mv Sánchez-Grande, Ana
Urgel, José
García Benito, Inés
Santos Barahona, José Manuel
Biswas, Kalyan
Lauwaet, Koen
Gallego, José M.
Rosen, Johanna
Miranda, Rodolfo
Björk, Jonas
Martín León, Nazario
Écija, David
author Sánchez-Grande, Ana
author_facet Sánchez-Grande, Ana
Urgel, José
García Benito, Inés
Santos Barahona, José Manuel
Biswas, Kalyan
Lauwaet, Koen
Gallego, José M.
Rosen, Johanna
Miranda, Rodolfo
Björk, Jonas
Martín León, Nazario
Écija, David
author_role author
author2 Urgel, José
García Benito, Inés
Santos Barahona, José Manuel
Biswas, Kalyan
Lauwaet, Koen
Gallego, José M.
Rosen, Johanna
Miranda, Rodolfo
Björk, Jonas
Martín León, Nazario
Écija, David
author2_role author
author
author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Universidad Complutense de Madrid
dc.subject.none.fl_str_mv 547
Química orgánica (Química)
2306 Química Orgánica
topic 547
Química orgánica (Química)
2306 Química Orgánica
description On‐surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N‐containing pentacene‐based precursor (tetraazapentacene) is ex‐professo synthesized endowed with terminal dibromomethylene (:CBr<jats:sub>2</jats:sub>) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N‐containing conjugated coordination polymer (P1). Subsequently, P1undergoes ladderization at 200 °C, affording a pyrrolopyrrole‐bridged conjugated polymer (P2). On Au(111) the formation of the intermediate polymer P1 is not observed and, instead, after annealing at 100 °C, the conjugated ladder polymer P2 is obtained, revealing the crucial role of metal adatoms on Ag(111) as compared to Au(111). Finally, on Ag(100) the loss of :CBr2 groups affords the formation of tetraazapentacene monomers, which coexist with polymer P1. Our results contribute to introduce protocols for the synthesis of N‐containing conjugated polymers, illustrating the selective role of the metallic support in the underlying reaction mechanisms.</jats:p>
publishDate 2022
dc.date.none.fl_str_mv 2022
2022-01-01
2022
2022-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/20.500.14352/93405
url https://hdl.handle.net/20.500.14352/93405
dc.language.none.fl_str_mv Español
spa
language_invalid_str_mv Español
language spa
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/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-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:Docta Complutense
instname:Universidad Complutense de Madrid (UCM)
instname_str Universidad Complutense de Madrid (UCM)
reponame_str Docta Complutense
collection Docta Complutense
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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