Low-lying LUMO boosts conductance in antiaromatic dibenzopentalene versus aromatic analogues

Antiaromaticity is a fundamental concept in chemistry, but the study of molecular wires incorporating antiaromatic units is limited. Despite initial predictions, very few studies show that antiaromaticity has a beneficial effect on electron transport. Dibenzo[a,e]pentalene (DBP) is a stable structur...

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Autores: Schmidt, Maximilian, Esser, Birgit, Leary, Edmund, Abellán Vicente, Lydia, González, M. Teresa, Zotti, Linda Ángela
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:10486/714504
Acesso em linha:http://hdl.handle.net/10486/714504
https://dx.doi.org/10.1002/chem.202400935
Access Level:Acceso aberto
Palavra-chave:antiaromaticity
break junction
dibenzopentalene
pyridyl anchor groups
single-molecule conductance
Física
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spelling Low-lying LUMO boosts conductance in antiaromatic dibenzopentalene versus aromatic analoguesSchmidt, MaximilianEsser, BirgitLeary, EdmundAbellán Vicente, LydiaGonzález, M. TeresaZotti, Linda Ángelaantiaromaticitybreak junctiondibenzopentalenepyridyl anchor groupssingle-molecule conductanceFísicaAntiaromaticity is a fundamental concept in chemistry, but the study of molecular wires incorporating antiaromatic units is limited. Despite initial predictions, very few studies show that antiaromaticity has a beneficial effect on electron transport. Dibenzo[a,e]pentalene (DBP) is a stable structure that displays appreciable antiaromaticity within the five-membered rings of the pentalene core. We have investigated derivatives of DBP furnished with pyridyl (Py) and F4-pyridyl (PyF4) anchor groups, and compared the conductance with purely aromatic phenyl and anthracene analogues. We find that the low-bias conductance of DBP-Py is approximately 60 % larger than that of the anthracene analogue Anth-Py and 250 % larger compared to the phenyl derivative Ph-Py. This is due to a better alignment of the LUMO with the gold Fermi level, which we confirm by conductance-voltage spectroscopy where the conductance of DBP-Py shows the greatest voltage-dependence. The F4-pyridyl compounds, which have lower LUMO energies compared to the pyridyl analogues, did not, however, form detectable molecular junctions. The strongly electron-withdrawing fluorine atoms reduce the donor capability of the nitrogen lone-pair to the point where stable N−Au bonds no longer formEL thanks the Comunidad de Madrid Atracci\u00F3n de Talento grant 2019\u2010T1/IND\u201016384 and from the Spanish MCIN (MCIN/AEI/10.13039/501100011033) PID2021\u2010127964NB\u2010C21 and CNS2023\u2010145464. IMDEA Nanociencia acknowledges support from the \u2032Severo Ochoa\u2032 Programme for Centres of Excellence in R&D (CEX2020\u2010001039\u2010S). TG thanks NanomagCOST\u2010CM (S2018/NMT\u20104321) and DECOSMOL (EIGConcertJapan). This project was funded by the German Research Foundation (DFG) under Project ID 441236036 and through grant no INST 40/575\u20101 FUGG (JUSTUS 2 cluster). We acknowledge financial support through the state of Baden\u2010W\u00FCrttemberg through bwHPC. LAZ thanks the Spanish MCIN/AEI/10.13039/ 501100011033 for the grant PID2021\u2010125604NB\u2010I00 and the \u201CMar\u00EDa de Maeztu\u201D Programme for Units of Excellence in R&D (CEX2023\u2010001316\u2010M). Open Access funding enabled and organized by Projekt DEAL.WileyDepartamento de Física Teórica de la Materia CondensadaFacultad de Ciencias20242024-07-16research articlehttp://purl.org/coar/resource_type/c_2df8fbb1EVoRhttp://purl.org/coar/version/c_dc82b40f9837b551info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/714504https://dx.doi.org/10.1002/chem.202400935reponame: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:10486/7145042026-06-23T12:46:27Z
dc.title.none.fl_str_mv Low-lying LUMO boosts conductance in antiaromatic dibenzopentalene versus aromatic analogues
title Low-lying LUMO boosts conductance in antiaromatic dibenzopentalene versus aromatic analogues
spellingShingle Low-lying LUMO boosts conductance in antiaromatic dibenzopentalene versus aromatic analogues
Schmidt, Maximilian
antiaromaticity
break junction
dibenzopentalene
pyridyl anchor groups
single-molecule conductance
Física
title_short Low-lying LUMO boosts conductance in antiaromatic dibenzopentalene versus aromatic analogues
title_full Low-lying LUMO boosts conductance in antiaromatic dibenzopentalene versus aromatic analogues
title_fullStr Low-lying LUMO boosts conductance in antiaromatic dibenzopentalene versus aromatic analogues
title_full_unstemmed Low-lying LUMO boosts conductance in antiaromatic dibenzopentalene versus aromatic analogues
title_sort Low-lying LUMO boosts conductance in antiaromatic dibenzopentalene versus aromatic analogues
dc.creator.none.fl_str_mv Schmidt, Maximilian
Esser, Birgit
Leary, Edmund
Abellán Vicente, Lydia
González, M. Teresa
Zotti, Linda Ángela
author Schmidt, Maximilian
author_facet Schmidt, Maximilian
Esser, Birgit
Leary, Edmund
Abellán Vicente, Lydia
González, M. Teresa
Zotti, Linda Ángela
author_role author
author2 Esser, Birgit
Leary, Edmund
Abellán Vicente, Lydia
González, M. Teresa
Zotti, Linda Ángela
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Departamento de Física Teórica de la Materia Condensada
Facultad de Ciencias
dc.subject.none.fl_str_mv antiaromaticity
break junction
dibenzopentalene
pyridyl anchor groups
single-molecule conductance
Física
topic antiaromaticity
break junction
dibenzopentalene
pyridyl anchor groups
single-molecule conductance
Física
description Antiaromaticity is a fundamental concept in chemistry, but the study of molecular wires incorporating antiaromatic units is limited. Despite initial predictions, very few studies show that antiaromaticity has a beneficial effect on electron transport. Dibenzo[a,e]pentalene (DBP) is a stable structure that displays appreciable antiaromaticity within the five-membered rings of the pentalene core. We have investigated derivatives of DBP furnished with pyridyl (Py) and F4-pyridyl (PyF4) anchor groups, and compared the conductance with purely aromatic phenyl and anthracene analogues. We find that the low-bias conductance of DBP-Py is approximately 60 % larger than that of the anthracene analogue Anth-Py and 250 % larger compared to the phenyl derivative Ph-Py. This is due to a better alignment of the LUMO with the gold Fermi level, which we confirm by conductance-voltage spectroscopy where the conductance of DBP-Py shows the greatest voltage-dependence. The F4-pyridyl compounds, which have lower LUMO energies compared to the pyridyl analogues, did not, however, form detectable molecular junctions. The strongly electron-withdrawing fluorine atoms reduce the donor capability of the nitrogen lone-pair to the point where stable N−Au bonds no longer form
publishDate 2024
dc.date.none.fl_str_mv 2024
2024-07-16
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
EVoR
http://purl.org/coar/version/c_dc82b40f9837b551
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10486/714504
https://dx.doi.org/10.1002/chem.202400935
url http://hdl.handle.net/10486/714504
https://dx.doi.org/10.1002/chem.202400935
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
publisher.none.fl_str_mv Wiley
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 15.812429

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