Understanding Kinetically Controlled Spin Transitions in Bistable Spin Crossover Materials

Spin crossover (SCO) materials can be kinetically trapped in a photo-excited metastable state in the so-called LIESST and reverse-LIESST processes. Under these conditions, SCO molecules are excellent light-responsive bistable molecular switches. However, above a certain temperature (TLIESST and Tr-L...

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Autores: Vela Llausí, Sergi, Fumanal Quintana, María, Sousa Romero, Carmen
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/225250
Acceso en línea:https://hdl.handle.net/2445/225250
Access Level:acceso abierto
Palabra clave:Cinètica química
Ciència dels materials
Compostos de coordinació
Chemical kinetics
Materials science
Coordination compounds
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spelling Understanding Kinetically Controlled Spin Transitions in Bistable Spin Crossover MaterialsVela Llausí, SergiFumanal Quintana, MaríaSousa Romero, CarmenCinètica químicaCiència dels materialsCompostos de coordinacióChemical kineticsMaterials scienceCoordination compoundsSpin crossover (SCO) materials can be kinetically trapped in a photo-excited metastable state in the so-called LIESST and reverse-LIESST processes. Under these conditions, SCO molecules are excellent light-responsive bistable molecular switches. However, above a certain temperature (TLIESST and Tr-LIESST, respectively), the relaxation to the ground state becomes favorable and their bistability is suppressed. Understanding the mechanism of these processes, and being able to predict their kinetics, is key to designing SCO switches that are able to operate at room temperature. Herein, we reveal the mechanism of thermally induced spin transitions of the [FeII(1-bpp)2]2+ SCO complex, and we predict its TLIESST (as well as its T1/2) with unprecedented accuracy. This is possible here thanks to the efficient reconstruction of the low-spin (LS, S = 0), high-spin (HS, S = 2) and intermediate (IS, S = 1) state Free energy surfaces (FESs) with ab initio and machine-learning methods, and the characterization of the minimum energy crossing points (MECPs) connecting those FESs. This approach paves the way for the systematic investigation of molecular features determining the mechanism of kinetically controlled transitions in SCO materials, as well as their temperature-dependent rate constants.Royal Society of Chemistry2023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://hdl.handle.net/2445/225250Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésReproducció del document publicat a: https://doi.org/10.1039/D2TC04266EJournal of Materials Chemistry C, 2023, vol. 11, p. 235-243https://doi.org/10.1039/D2TC04266Ecc-by-nd (c) Vela, S. et al., 2023http://creativecommons.org/licenses/by-nd/3.0/info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/2252502026-05-27T06:46:51Z
dc.title.none.fl_str_mv Understanding Kinetically Controlled Spin Transitions in Bistable Spin Crossover Materials
title Understanding Kinetically Controlled Spin Transitions in Bistable Spin Crossover Materials
spellingShingle Understanding Kinetically Controlled Spin Transitions in Bistable Spin Crossover Materials
Vela Llausí, Sergi
Cinètica química
Ciència dels materials
Compostos de coordinació
Chemical kinetics
Materials science
Coordination compounds
title_short Understanding Kinetically Controlled Spin Transitions in Bistable Spin Crossover Materials
title_full Understanding Kinetically Controlled Spin Transitions in Bistable Spin Crossover Materials
title_fullStr Understanding Kinetically Controlled Spin Transitions in Bistable Spin Crossover Materials
title_full_unstemmed Understanding Kinetically Controlled Spin Transitions in Bistable Spin Crossover Materials
title_sort Understanding Kinetically Controlled Spin Transitions in Bistable Spin Crossover Materials
dc.creator.none.fl_str_mv Vela Llausí, Sergi
Fumanal Quintana, María
Sousa Romero, Carmen
author Vela Llausí, Sergi
author_facet Vela Llausí, Sergi
Fumanal Quintana, María
Sousa Romero, Carmen
author_role author
author2 Fumanal Quintana, María
Sousa Romero, Carmen
author2_role author
author
dc.subject.none.fl_str_mv Cinètica química
Ciència dels materials
Compostos de coordinació
Chemical kinetics
Materials science
Coordination compounds
topic Cinètica química
Ciència dels materials
Compostos de coordinació
Chemical kinetics
Materials science
Coordination compounds
description Spin crossover (SCO) materials can be kinetically trapped in a photo-excited metastable state in the so-called LIESST and reverse-LIESST processes. Under these conditions, SCO molecules are excellent light-responsive bistable molecular switches. However, above a certain temperature (TLIESST and Tr-LIESST, respectively), the relaxation to the ground state becomes favorable and their bistability is suppressed. Understanding the mechanism of these processes, and being able to predict their kinetics, is key to designing SCO switches that are able to operate at room temperature. Herein, we reveal the mechanism of thermally induced spin transitions of the [FeII(1-bpp)2]2+ SCO complex, and we predict its TLIESST (as well as its T1/2) with unprecedented accuracy. This is possible here thanks to the efficient reconstruction of the low-spin (LS, S = 0), high-spin (HS, S = 2) and intermediate (IS, S = 1) state Free energy surfaces (FESs) with ab initio and machine-learning methods, and the characterization of the minimum energy crossing points (MECPs) connecting those FESs. This approach paves the way for the systematic investigation of molecular features determining the mechanism of kinetically controlled transitions in SCO materials, as well as their temperature-dependent rate constants.
publishDate 2023
dc.date.none.fl_str_mv 2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/225250
url https://hdl.handle.net/2445/225250
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Reproducció del document publicat a: https://doi.org/10.1039/D2TC04266E
Journal of Materials Chemistry C, 2023, vol. 11, p. 235-243
https://doi.org/10.1039/D2TC04266E
dc.rights.none.fl_str_mv cc-by-nd (c) Vela, S. et al., 2023
http://creativecommons.org/licenses/by-nd/3.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv cc-by-nd (c) Vela, S. et al., 2023
http://creativecommons.org/licenses/by-nd/3.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv Articles publicats en revistes (Ciència dels Materials i Química Física)
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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