Lattice-solvent effects in the spin-crossover of an Fe(II)-based material. The key role of intermolecular interactions between solvent molecules

The spin transition of Fe(II) complexes is the subject of intensive synthetic and computational efforts. In this manuscript, we analyze the spin crossover (SCO) of [Fe(Edpsp)(2)](2+) (1), which features a spin transition depending on the cocrystallizing solvent molecules. Whereas the use of acetone...

ver descrição completa

Detalhes bibliográficos
Autores: Fumanal Quintana, María, Jimenez-Gravalos, Fernando, Ribas Ariño, Jordi, Vela Llausí, Sergi
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
País:España
Recursos:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/154496
Acesso em linha:https://hdl.handle.net/2445/154496
Access Level:acceso abierto
Palavra-chave:Ferro
Lligands
Dissolvents
Iron
Ligands
Solvents
id ES_532a885e4dd2ae6d38c40e44cf29ee90
oai_identifier_str oai:recercat.cat:2445/154496
network_acronym_str ES
network_name_str España
repository_id_str
spelling Lattice-solvent effects in the spin-crossover of an Fe(II)-based material. The key role of intermolecular interactions between solvent moleculesFumanal Quintana, MaríaJimenez-Gravalos, FernandoRibas Ariño, JordiVela Llausí, SergiFerroLligandsDissolventsIronLigandsSolventsThe spin transition of Fe(II) complexes is the subject of intensive synthetic and computational efforts. In this manuscript, we analyze the spin crossover (SCO) of [Fe(Edpsp)(2)](2+) (1), which features a spin transition depending on the cocrystallizing solvent molecules. Whereas the use of acetone results in a hysteretic spin transition at similar to 170 K, the use of propylene carbonate (PC) results in a permanent diamagnetic signal up to 300 K. By means of DFT+U+D2 calculations in the solid state of the material, we unravel the reasons for such different behavior. Our results allow us to ascribe the relatively low transition temperature of 1(BF4)(2.) acetone to the distorted arrangement of the SCO molecules in the low-spin state of the material. In turn, intermolecular interactions play the primary role in the case of 1(BF4)(2).2PC. In particular, we found that solvent-solvent interactions actively promote the stability of the low-spin state due to the formation of PC dimers. These dimers would appear at larger distances in the high-spin phase, with the subsequent loss of phase stability. This is yet another proof of how subtle is the spin transition phenomenon in Fe(II)-based architectures.American Chemical Society2020202020172020info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion10 p.application/pdfhttps://hdl.handle.net/2445/154496Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésVersió postprint del document publicat a: https://doi.org/10.1021/acs.inorgchem.7b00017Inorganic Chemistry, 2017, vol. 56, num. 8, p. 4474-4483https://doi.org/10.1021/acs.inorgchem.7b00017(c) American Chemical Society , 2017info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1544962026-05-29T05:05:01Z
dc.title.none.fl_str_mv Lattice-solvent effects in the spin-crossover of an Fe(II)-based material. The key role of intermolecular interactions between solvent molecules
title Lattice-solvent effects in the spin-crossover of an Fe(II)-based material. The key role of intermolecular interactions between solvent molecules
spellingShingle Lattice-solvent effects in the spin-crossover of an Fe(II)-based material. The key role of intermolecular interactions between solvent molecules
Fumanal Quintana, María
Ferro
Lligands
Dissolvents
Iron
Ligands
Solvents
title_short Lattice-solvent effects in the spin-crossover of an Fe(II)-based material. The key role of intermolecular interactions between solvent molecules
title_full Lattice-solvent effects in the spin-crossover of an Fe(II)-based material. The key role of intermolecular interactions between solvent molecules
title_fullStr Lattice-solvent effects in the spin-crossover of an Fe(II)-based material. The key role of intermolecular interactions between solvent molecules
title_full_unstemmed Lattice-solvent effects in the spin-crossover of an Fe(II)-based material. The key role of intermolecular interactions between solvent molecules
title_sort Lattice-solvent effects in the spin-crossover of an Fe(II)-based material. The key role of intermolecular interactions between solvent molecules
dc.creator.none.fl_str_mv Fumanal Quintana, María
Jimenez-Gravalos, Fernando
Ribas Ariño, Jordi
Vela Llausí, Sergi
author Fumanal Quintana, María
author_facet Fumanal Quintana, María
Jimenez-Gravalos, Fernando
Ribas Ariño, Jordi
Vela Llausí, Sergi
author_role author
author2 Jimenez-Gravalos, Fernando
Ribas Ariño, Jordi
Vela Llausí, Sergi
author2_role author
author
author
dc.subject.none.fl_str_mv Ferro
Lligands
Dissolvents
Iron
Ligands
Solvents
topic Ferro
Lligands
Dissolvents
Iron
Ligands
Solvents
description The spin transition of Fe(II) complexes is the subject of intensive synthetic and computational efforts. In this manuscript, we analyze the spin crossover (SCO) of [Fe(Edpsp)(2)](2+) (1), which features a spin transition depending on the cocrystallizing solvent molecules. Whereas the use of acetone results in a hysteretic spin transition at similar to 170 K, the use of propylene carbonate (PC) results in a permanent diamagnetic signal up to 300 K. By means of DFT+U+D2 calculations in the solid state of the material, we unravel the reasons for such different behavior. Our results allow us to ascribe the relatively low transition temperature of 1(BF4)(2.) acetone to the distorted arrangement of the SCO molecules in the low-spin state of the material. In turn, intermolecular interactions play the primary role in the case of 1(BF4)(2).2PC. In particular, we found that solvent-solvent interactions actively promote the stability of the low-spin state due to the formation of PC dimers. These dimers would appear at larger distances in the high-spin phase, with the subsequent loss of phase stability. This is yet another proof of how subtle is the spin transition phenomenon in Fe(II)-based architectures.
publishDate 2017
dc.date.none.fl_str_mv 2017
2020
2020
2020
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/154496
url https://hdl.handle.net/2445/154496
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1021/acs.inorgchem.7b00017
Inorganic Chemistry, 2017, vol. 56, num. 8, p. 4474-4483
https://doi.org/10.1021/acs.inorgchem.7b00017
dc.rights.none.fl_str_mv (c) American Chemical Society , 2017
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) American Chemical Society , 2017
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 10 p.
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv Articles publicats en revistes (Ciència dels Materials i Química Física)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869408098578333696
score 15,812455

Registos relacionados