Dinuclear enantiopure Ln3+ complexes with (S-) and (R-) 2-phenylbutyrate ligands. Luminescence, CPL and magnetic properties

The reaction of Ln(NO3)2·6H2O (Ln = Nd, Sm, Eu, Tb, Dy, Tm and Yb) with the respective enantiopure (R)-(−)-2-phenylbutyric or (S)-(+)-2-phenylbutyric acid (R/S-2-HPhBut) and 4,7-diphenyl-1,10-phenanthroline (Bphen) allows the isolation of chiral dinuclear compounds of the formula [Ln2(μ-R/S-2-PhBut)...

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Autores: Tubau Ribot, Ànnia, Zinna, Francesco, Di Bari, Lorenzo, Font Bardia, Ma. Mercedes, Vicente Castillo, Ramón
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2024
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:dnet:ubarcelona__::9f97e601598f3ae6a47b35e499323020
Acceso en línea:https://hdl.handle.net/2445/229579
Access Level:acceso abierto
Palabra clave:Propietats magnètiques
Compostos intermetàl·lics
Magnetic properties
Intermetallic compounds
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spelling Dinuclear enantiopure Ln3+ complexes with (S-) and (R-) 2-phenylbutyrate ligands. Luminescence, CPL and magnetic propertiesDinuclear enantiopure Ln$^{3+}$ complexes with ($S$)- and ($R$)-2-phenylbutyrate ligands. Luminescence, CPL and magnetic propertiesTubau Ribot, ÀnniaZinna, FrancescoDi Bari, LorenzoFont Bardia, Ma. MercedesVicente Castillo, RamónPropietats magnètiquesCompostos intermetàl·licsMagnetic propertiesIntermetallic compoundsThe reaction of Ln(NO3)2·6H2O (Ln = Nd, Sm, Eu, Tb, Dy, Tm and Yb) with the respective enantiopure (R)-(−)-2-phenylbutyric or (S)-(+)-2-phenylbutyric acid (R/S-2-HPhBut) and 4,7-diphenyl-1,10-phenanthroline (Bphen) allows the isolation of chiral dinuclear compounds of the formula [Ln2(μ-R/S-2-PhBut)4(R/S-2PhBut)2(Bphen)2] where Ln = Nd3+ (R/S-Nd-a), Sm3+ (R/S-Sm-a), Eu3+ (R/S-Eu-a), Tb3+ (R/S-Tb-a and R/S-Tb-b), Dy3+ (R/S-Dy-a and R/S-Dy-b), Tm3+ (R/S-Tm-b) and Yb3+ (R/S-Yb-b). Single crystal X-ray diffraction was performed for compounds S-Eu-a and S-Tm-b. Powder crystal X-ray diffraction was performed for all complexes. From the crystallographic data two different structural motifs were found which are referred to as structure type a and structure type b. In structure type a, the Ln3+ atoms are bridged through four R or S-2-PhBut ligands with two different kinds of coordination modes whereas in structure type b the two Ln3+ atoms are bridged through four R or S-2-PhBut ligands showing only one kind of coordination mode. For those lanthanide ions exhibiting both structure types, Tb3+ and Dy3+, a difference in the luminescence and magnetism behavior is observed. All compounds (except R/S-Tm-b) exhibit sensitized luminescence, notably the Eu3+ and Tb3+ analogues. Circular Dichroism (CD) and Circular Polarized Luminescence (CPL) in the solid state and in 1 mM dichloromethane (DCM) solutions are reported, leading to improved chiroptical properties for the DCM solutions. The asymmetry factor (glum) in 1 mM DCM is ±0.02 (+ for R-Eu-a) for the magnetically allowed transition 5D0 → 7F1 and ±0.03 (+ for R-Tb-a and R-Tb-b) for the 5D4 → 7F5 transition. Magnetic properties of all compounds were studied and the Dy3+ compound with the structural motif b (R-Dy-b) shows Single Molecular Magnet (SMM) behavior under a 0 T magnetic field. However, R-Dy-a is a field-induced SMM.Royal Society of Chemistry2024info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://hdl.handle.net/2445/229579Articles publicats en revistes (Química Inorgànica i Orgànica)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésReproducció del document publicat a: https://doi.org/10.1039/d4dt01295jDalton Transactions, 2024, vol. 53, num.32, p. 13566-13582https://doi.org/10.1039/d4dt01295jcc by-nc (c) Tubau, I. et al., 2024https://creativecommons.org/licenses/by-nc/3.0/info:eu-repo/semantics/openAccessoai:dnet:ubarcelona__::9f97e601598f3ae6a47b35e4993230202026-05-27T06:46:51Z
dc.title.none.fl_str_mv Dinuclear enantiopure Ln3+ complexes with (S-) and (R-) 2-phenylbutyrate ligands. Luminescence, CPL and magnetic properties
Dinuclear enantiopure Ln$^{3+}$ complexes with ($S$)- and ($R$)-2-phenylbutyrate ligands. Luminescence, CPL and magnetic properties
title Dinuclear enantiopure Ln3+ complexes with (S-) and (R-) 2-phenylbutyrate ligands. Luminescence, CPL and magnetic properties
spellingShingle Dinuclear enantiopure Ln3+ complexes with (S-) and (R-) 2-phenylbutyrate ligands. Luminescence, CPL and magnetic properties
Tubau Ribot, Ànnia
Propietats magnètiques
Compostos intermetàl·lics
Magnetic properties
Intermetallic compounds
title_short Dinuclear enantiopure Ln3+ complexes with (S-) and (R-) 2-phenylbutyrate ligands. Luminescence, CPL and magnetic properties
title_full Dinuclear enantiopure Ln3+ complexes with (S-) and (R-) 2-phenylbutyrate ligands. Luminescence, CPL and magnetic properties
title_fullStr Dinuclear enantiopure Ln3+ complexes with (S-) and (R-) 2-phenylbutyrate ligands. Luminescence, CPL and magnetic properties
title_full_unstemmed Dinuclear enantiopure Ln3+ complexes with (S-) and (R-) 2-phenylbutyrate ligands. Luminescence, CPL and magnetic properties
title_sort Dinuclear enantiopure Ln3+ complexes with (S-) and (R-) 2-phenylbutyrate ligands. Luminescence, CPL and magnetic properties
dc.creator.none.fl_str_mv Tubau Ribot, Ànnia
Zinna, Francesco
Di Bari, Lorenzo
Font Bardia, Ma. Mercedes
Vicente Castillo, Ramón
author Tubau Ribot, Ànnia
author_facet Tubau Ribot, Ànnia
Zinna, Francesco
Di Bari, Lorenzo
Font Bardia, Ma. Mercedes
Vicente Castillo, Ramón
author_role author
author2 Zinna, Francesco
Di Bari, Lorenzo
Font Bardia, Ma. Mercedes
Vicente Castillo, Ramón
author2_role author
author
author
author
dc.subject.none.fl_str_mv Propietats magnètiques
Compostos intermetàl·lics
Magnetic properties
Intermetallic compounds
topic Propietats magnètiques
Compostos intermetàl·lics
Magnetic properties
Intermetallic compounds
description The reaction of Ln(NO3)2·6H2O (Ln = Nd, Sm, Eu, Tb, Dy, Tm and Yb) with the respective enantiopure (R)-(−)-2-phenylbutyric or (S)-(+)-2-phenylbutyric acid (R/S-2-HPhBut) and 4,7-diphenyl-1,10-phenanthroline (Bphen) allows the isolation of chiral dinuclear compounds of the formula [Ln2(μ-R/S-2-PhBut)4(R/S-2PhBut)2(Bphen)2] where Ln = Nd3+ (R/S-Nd-a), Sm3+ (R/S-Sm-a), Eu3+ (R/S-Eu-a), Tb3+ (R/S-Tb-a and R/S-Tb-b), Dy3+ (R/S-Dy-a and R/S-Dy-b), Tm3+ (R/S-Tm-b) and Yb3+ (R/S-Yb-b). Single crystal X-ray diffraction was performed for compounds S-Eu-a and S-Tm-b. Powder crystal X-ray diffraction was performed for all complexes. From the crystallographic data two different structural motifs were found which are referred to as structure type a and structure type b. In structure type a, the Ln3+ atoms are bridged through four R or S-2-PhBut ligands with two different kinds of coordination modes whereas in structure type b the two Ln3+ atoms are bridged through four R or S-2-PhBut ligands showing only one kind of coordination mode. For those lanthanide ions exhibiting both structure types, Tb3+ and Dy3+, a difference in the luminescence and magnetism behavior is observed. All compounds (except R/S-Tm-b) exhibit sensitized luminescence, notably the Eu3+ and Tb3+ analogues. Circular Dichroism (CD) and Circular Polarized Luminescence (CPL) in the solid state and in 1 mM dichloromethane (DCM) solutions are reported, leading to improved chiroptical properties for the DCM solutions. The asymmetry factor (glum) in 1 mM DCM is ±0.02 (+ for R-Eu-a) for the magnetically allowed transition 5D0 → 7F1 and ±0.03 (+ for R-Tb-a and R-Tb-b) for the 5D4 → 7F5 transition. Magnetic properties of all compounds were studied and the Dy3+ compound with the structural motif b (R-Dy-b) shows Single Molecular Magnet (SMM) behavior under a 0 T magnetic field. However, R-Dy-a is a field-induced SMM.
publishDate 2024
dc.date.none.fl_str_mv 2024
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/2445/229579
url https://hdl.handle.net/2445/229579
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/d4dt01295j
Dalton Transactions, 2024, vol. 53, num.32, p. 13566-13582
https://doi.org/10.1039/d4dt01295j
dc.rights.none.fl_str_mv cc by-nc (c) Tubau, I. et al., 2024
https://creativecommons.org/licenses/by-nc/3.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv cc by-nc (c) Tubau, I. et al., 2024
https://creativecommons.org/licenses/by-nc/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 (Química Inorgànica i Orgànica)
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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