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 (:CBr2) groups...
| Autores: | , , , , , , , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Fecha de publicación: | 2022 |
| País: | España |
| Institución: | Universidad Autónoma de Madrid |
| Repositorio: | Biblos-e Archivo. Repositorio Institucional de la UAM |
| Idioma: | inglés |
| OAI Identifier: | oai:repositorio.uam.es:10486/714141 |
| Acceso en línea: | http://hdl.handle.net/10486/714141 https://dx.doi.org/10.1002/advs.202200407 |
| Access Level: | acceso abierto |
| Palabra clave: | Conjugated polymers N-heteroacenes On-surface synthesis Scanning probe microscopies Física |
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Surface-assisted synthesis of N-Containing π-conjugated polymersSánchez-Grande, AnaUrgel, José I.García-Benito, InésSantos, JoséGallego, José M.Rosen, JohannaMartín, NazarioÉcija, DavidBiswas, KalyanLauwaet, KoenBjörk, JonasMiranda Soriano, RodolfoConjugated polymersN-heteroacenesOn-surface synthesisScanning probe microscopiesFísicaOn-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 (:CBr2) 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, P1 undergoes 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 mechanismsThe authors acknowledge the European Research Council (ERC CoG ELEC-NANO nº 766555), the Comunidad de Madrid [project QUIMTRONIC-CM(Y2018/NMT-4783)] and Ministerio de Ciencia e Innovación (PID2019-108532GB-I00). IMDEA Nanociencia thanks support from the “SeveroOchoa” Programme for Centers of Excellence in R&D (MINECO, GrantSEV-2016-0686)Wiley-VCH GmbHDepartamento de Física de la Materia CondensadaFacultad de Ciencias20222022-07-01research articlehttp://purl.org/coar/resource_type/c_2df8fbb1VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/714141https://dx.doi.org/10.1002/advs.202200407reponame: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:10486/7141412026-06-23T12:46:27Z |
| 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 Conjugated polymers N-heteroacenes On-surface synthesis Scanning probe microscopies Física |
| 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 I. García-Benito, Inés Santos, José Gallego, José M. Rosen, Johanna Martín, Nazario Écija, David Biswas, Kalyan Lauwaet, Koen Björk, Jonas Miranda Soriano, Rodolfo |
| author |
Sánchez-Grande, Ana |
| author_facet |
Sánchez-Grande, Ana Urgel, José I. García-Benito, Inés Santos, José Gallego, José M. Rosen, Johanna Martín, Nazario Écija, David Biswas, Kalyan Lauwaet, Koen Björk, Jonas Miranda Soriano, Rodolfo |
| author_role |
author |
| author2 |
Urgel, José I. García-Benito, Inés Santos, José Gallego, José M. Rosen, Johanna Martín, Nazario Écija, David Biswas, Kalyan Lauwaet, Koen Björk, Jonas Miranda Soriano, Rodolfo |
| author2_role |
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 |
Conjugated polymers N-heteroacenes On-surface synthesis Scanning probe microscopies Física |
| topic |
Conjugated polymers N-heteroacenes On-surface synthesis Scanning probe microscopies Física |
| 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 (:CBr2) 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, P1 undergoes 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 |
| publishDate |
2022 |
| dc.date.none.fl_str_mv |
2022 2022-07-01 |
| 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/10486/714141 https://dx.doi.org/10.1002/advs.202200407 |
| url |
http://hdl.handle.net/10486/714141 https://dx.doi.org/10.1002/advs.202200407 |
| 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 |
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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 |
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Biblos-e Archivo. Repositorio Institucional de la UAM |
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1869404546024865792 |
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15,81155 |