Spin Crossover-Assisted Modulation of Electron Transport in a Single-Crystal 3D Metal-Organic Framework

Molecule-based spin crossover (SCO) materials display likely one of the most spectacular switchable processes. The SCO involves reversible changes in their physicochemical properties (i.e. optical, magnetic, electronic, and elastic) that are coupled with the spin-state change under an external pertu...

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Autores: Martinez-Martinez, Ana|||0000-0002-2252-955X, Resines-Urien, Esther|||0000-0002-1929-4681, Piñeiro-López, Lucía, Fernández-Blanco, Angel, Mariano, Antonio Lorenzo|||0000-0002-1282-4977, Albalad, Jorge|||0000-0001-5850-6723, Maspoch Comamala, Daniel|||0000-0003-1325-9161, Poloni, Roberta, Rodríguez-Velamazán, Jose Alberto|||0000-0002-8505-5232, Sañudo, E. Carolina|||0000-0001-9647-6406, Burzurí, Enrique|||0000-0001-7906-7192, Sánchez Costa, José|||0000-0001-5426-7956
Formato: artículo
Fecha de publicación:2023
País:España
Recursos:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:302230
Acesso em linha:https://ddd.uab.cat/record/302230
https://dx.doi.org/urn:doi:10.1021/acs.chemmater.3c01049
Access Level:acceso abierto
Palavra-chave:3d metals
Electron transport
Metalorganic frameworks (MOFs)
Optical-
Physicochemical property
Reversible change
Spin crossover materials
Spin crossovers
Spin-state changes
Switchable
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spelling Spin Crossover-Assisted Modulation of Electron Transport in a Single-Crystal 3D Metal-Organic FrameworkMartinez-Martinez, Ana|||0000-0002-2252-955XResines-Urien, Esther|||0000-0002-1929-4681Piñeiro-López, LucíaFernández-Blanco, AngelMariano, Antonio Lorenzo|||0000-0002-1282-4977Albalad, Jorge|||0000-0001-5850-6723Maspoch Comamala, Daniel|||0000-0003-1325-9161Poloni, RobertaRodríguez-Velamazán, Jose Alberto|||0000-0002-8505-5232Sañudo, E. Carolina|||0000-0001-9647-6406Burzurí, Enrique|||0000-0001-7906-7192Sánchez Costa, José|||0000-0001-5426-79563d metalsElectron transportMetalorganic frameworks (MOFs)Optical-Physicochemical propertyReversible changeSpin crossover materialsSpin crossoversSpin-state changesSwitchableMolecule-based spin crossover (SCO) materials display likely one of the most spectacular switchable processes. The SCO involves reversible changes in their physicochemical properties (i.e. optical, magnetic, electronic, and elastic) that are coupled with the spin-state change under an external perturbation (i.e. temperature, light, magnetic field, or the inclusion/release of analytes). Although very promising for their future integration into electronic devices, most SCO compounds show two major drawbacks: (i) their intrinsic low conductance and (ii) the unclear mechanism connecting the spin-state change and the electrical conductivity. Herein, we report the controlled single-crystal-to-single-crystal temperature-induced transformation in a robust metal-organic framework, [Fe(Hbdt)]·9HO (1), being bdt = 1,4-benzeneditetrazolate, exhibiting a dynamic spin-state change concomitant with an increment in the anisotropic electrical conductance. Compound 1 remains intact during the SCO process even after approximately a 15% volume reduction. The experimental findings are rationalized by analyzing the electronic delocalization of the frontier states by means of density-functional theory calculations. The results point to a correlation between the spin-state of the iron and the electronic conductivity of the 3D structure. In addition, the reversibility of the process is proved. 22023-01-0120232023-01-01Articlehttp://purl.org/coar/resource_type/c_6501SMURhttp://purl.org/coar/version/c_71e4c1898caa6e32info:eu-repo/semantics/articleapplication/pdfhttps://ddd.uab.cat/record/302230https://dx.doi.org/urn:doi:10.1021/acs.chemmater.3c01049reponame:Dipòsit Digital de Documents de la UABinstname:Universitat Autònoma de BarcelonaInglésengAgencia Estatal de Investigación https://doi.org/10.13039/501100011033 PID2019-111479GB-I00Ministerio de Economía y Competitividad https://doi.org/10.13039/501100003329 RYC-2014-16866Ministerio de Economía y Competitividad https://doi.org/10.13039/501100003329 SEV-2016-0686Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 PGC2018-098630-B-I00Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 RTI2018-096075-A-C22Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 RYC2019-028429-Iopen accesshttp://purl.org/coar/access_right/c_abf2Aquest material està protegit per drets d'autor i/o drets afins. Podeu utilitzar aquest material en funció del que permet la legislació de drets d'autor i drets afins d'aplicació al vostre cas. Per a d'altres usos heu d'obtenir permís del(s) titular(s) de drets.https://rightsstatements.org/vocab/InC/1.0/info:eu-repo/semantics/openAccessoai:ddd.uab.cat:3022302026-06-06T12:50:31Z
dc.title.none.fl_str_mv Spin Crossover-Assisted Modulation of Electron Transport in a Single-Crystal 3D Metal-Organic Framework
title Spin Crossover-Assisted Modulation of Electron Transport in a Single-Crystal 3D Metal-Organic Framework
spellingShingle Spin Crossover-Assisted Modulation of Electron Transport in a Single-Crystal 3D Metal-Organic Framework
Martinez-Martinez, Ana|||0000-0002-2252-955X
3d metals
Electron transport
Metalorganic frameworks (MOFs)
Optical-
Physicochemical property
Reversible change
Spin crossover materials
Spin crossovers
Spin-state changes
Switchable
title_short Spin Crossover-Assisted Modulation of Electron Transport in a Single-Crystal 3D Metal-Organic Framework
title_full Spin Crossover-Assisted Modulation of Electron Transport in a Single-Crystal 3D Metal-Organic Framework
title_fullStr Spin Crossover-Assisted Modulation of Electron Transport in a Single-Crystal 3D Metal-Organic Framework
title_full_unstemmed Spin Crossover-Assisted Modulation of Electron Transport in a Single-Crystal 3D Metal-Organic Framework
title_sort Spin Crossover-Assisted Modulation of Electron Transport in a Single-Crystal 3D Metal-Organic Framework
dc.creator.none.fl_str_mv Martinez-Martinez, Ana|||0000-0002-2252-955X
Resines-Urien, Esther|||0000-0002-1929-4681
Piñeiro-López, Lucía
Fernández-Blanco, Angel
Mariano, Antonio Lorenzo|||0000-0002-1282-4977
Albalad, Jorge|||0000-0001-5850-6723
Maspoch Comamala, Daniel|||0000-0003-1325-9161
Poloni, Roberta
Rodríguez-Velamazán, Jose Alberto|||0000-0002-8505-5232
Sañudo, E. Carolina|||0000-0001-9647-6406
Burzurí, Enrique|||0000-0001-7906-7192
Sánchez Costa, José|||0000-0001-5426-7956
author Martinez-Martinez, Ana|||0000-0002-2252-955X
author_facet Martinez-Martinez, Ana|||0000-0002-2252-955X
Resines-Urien, Esther|||0000-0002-1929-4681
Piñeiro-López, Lucía
Fernández-Blanco, Angel
Mariano, Antonio Lorenzo|||0000-0002-1282-4977
Albalad, Jorge|||0000-0001-5850-6723
Maspoch Comamala, Daniel|||0000-0003-1325-9161
Poloni, Roberta
Rodríguez-Velamazán, Jose Alberto|||0000-0002-8505-5232
Sañudo, E. Carolina|||0000-0001-9647-6406
Burzurí, Enrique|||0000-0001-7906-7192
Sánchez Costa, José|||0000-0001-5426-7956
author_role author
author2 Resines-Urien, Esther|||0000-0002-1929-4681
Piñeiro-López, Lucía
Fernández-Blanco, Angel
Mariano, Antonio Lorenzo|||0000-0002-1282-4977
Albalad, Jorge|||0000-0001-5850-6723
Maspoch Comamala, Daniel|||0000-0003-1325-9161
Poloni, Roberta
Rodríguez-Velamazán, Jose Alberto|||0000-0002-8505-5232
Sañudo, E. Carolina|||0000-0001-9647-6406
Burzurí, Enrique|||0000-0001-7906-7192
Sánchez Costa, José|||0000-0001-5426-7956
author2_role author
author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv 3d metals
Electron transport
Metalorganic frameworks (MOFs)
Optical-
Physicochemical property
Reversible change
Spin crossover materials
Spin crossovers
Spin-state changes
Switchable
topic 3d metals
Electron transport
Metalorganic frameworks (MOFs)
Optical-
Physicochemical property
Reversible change
Spin crossover materials
Spin crossovers
Spin-state changes
Switchable
description Molecule-based spin crossover (SCO) materials display likely one of the most spectacular switchable processes. The SCO involves reversible changes in their physicochemical properties (i.e. optical, magnetic, electronic, and elastic) that are coupled with the spin-state change under an external perturbation (i.e. temperature, light, magnetic field, or the inclusion/release of analytes). Although very promising for their future integration into electronic devices, most SCO compounds show two major drawbacks: (i) their intrinsic low conductance and (ii) the unclear mechanism connecting the spin-state change and the electrical conductivity. Herein, we report the controlled single-crystal-to-single-crystal temperature-induced transformation in a robust metal-organic framework, [Fe(Hbdt)]·9HO (1), being bdt = 1,4-benzeneditetrazolate, exhibiting a dynamic spin-state change concomitant with an increment in the anisotropic electrical conductance. Compound 1 remains intact during the SCO process even after approximately a 15% volume reduction. The experimental findings are rationalized by analyzing the electronic delocalization of the frontier states by means of density-functional theory calculations. The results point to a correlation between the spin-state of the iron and the electronic conductivity of the 3D structure. In addition, the reversibility of the process is proved.
publishDate 2023
dc.date.none.fl_str_mv 2
2023-01-01
2023
2023-01-01
dc.type.none.fl_str_mv Article
http://purl.org/coar/resource_type/c_6501
SMUR
http://purl.org/coar/version/c_71e4c1898caa6e32
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://ddd.uab.cat/record/302230
https://dx.doi.org/urn:doi:10.1021/acs.chemmater.3c01049
url https://ddd.uab.cat/record/302230
https://dx.doi.org/urn:doi:10.1021/acs.chemmater.3c01049
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 PID2019-111479GB-I00
Ministerio de Economía y Competitividad https://doi.org/10.13039/501100003329 RYC-2014-16866
Ministerio de Economía y Competitividad https://doi.org/10.13039/501100003329 SEV-2016-0686
Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 PGC2018-098630-B-I00
Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 RTI2018-096075-A-C22
Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 RYC2019-028429-I
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
https://rightsstatements.org/vocab/InC/1.0/
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
https://rightsstatements.org/vocab/InC/1.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Dipòsit Digital de Documents de la UAB
instname:Universitat Autònoma de Barcelona
instname_str Universitat Autònoma de Barcelona
reponame_str Dipòsit Digital de Documents de la UAB
collection Dipòsit Digital de Documents de la UAB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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