Element-Selective Molecular Charge Transport Characteristics of Binuclear Copper(II)-Lanthanide(III) Complexes

A series of isostructural dinuclear 3d-4f complexes, isolated as [CuLn(L·SMe)2(OOCMe)2(NO3)]·xMeOH (Ln = Gd 1, Tb 2, Dy 3, and Y 4; x = 0.75-1) and comprising one acetate and two thioether-Schiff base (L·SMe-) bridging ligands based on 4-(methylthio)aniline and 2-hydroxy-3-methoxybenzaldehyde (HL·SM...

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Autores: Schmitz, Sebastian, Kovalchuk, Andrew, Martín Rodríguez, Alejandro, van Leusen, Jan, Izarova, Natalya V., Bourone, Svenja D. M., Ai, Yong, Ruiz Sabín, Eliseo, Chiechi, Ryan C., Kögerler, Paul, Monakhov, Kirill Yu.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Institución: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:2445/143967
Acceso en línea:https://hdl.handle.net/2445/143967
Access Level:acceso abierto
Palabra clave:Ions
Compostos complexos
Complex compounds
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spelling Element-Selective Molecular Charge Transport Characteristics of Binuclear Copper(II)-Lanthanide(III) ComplexesSchmitz, SebastianKovalchuk, AndrewMartín Rodríguez, Alejandrovan Leusen, JanIzarova, Natalya V.Bourone, Svenja D. M.Ai, YongRuiz Sabín, EliseoChiechi, Ryan C.Kögerler, PaulMonakhov, Kirill Yu.IonsCompostos complexosIonsComplex compoundsA series of isostructural dinuclear 3d-4f complexes, isolated as [CuLn(L·SMe)2(OOCMe)2(NO3)]·xMeOH (Ln = Gd 1, Tb 2, Dy 3, and Y 4; x = 0.75-1) and comprising one acetate and two thioether-Schiff base (L·SMe-) bridging ligands based on 4-(methylthio)aniline and 2-hydroxy-3-methoxybenzaldehyde (HL·SMe = C15H15NO2S), was synthesized and fully characterized. The magnetic properties of the charge-neutral {CuLn} complexes are dominated by ferromagnetic CuII-LnIII exchange interactions. Large-area electron transport studies reveal that the average conductivity of robust, self-assembled {CuLn} monolayers on a gold substrate is significantly lower than that of common alkanethiolates. Theoretical calculations of transmission spectra of individual complexes 1 and 4 embedded between two metallic electrodes show that the molecular current-voltage (I-V) characteristics are strongly influenced by electron transport through the Cu centers and thus fully independent of the lanthanide ion, in excellent agreement with the experimental I-V data for 1-4. The β-polarized transmission indicated by calculations of 1 and 4 points out their potential as spin filters. In addition, the reactivity of the title compound 1 with CuII in a square-pyramidal coordination environment toward methanolate and azide was examined, resulting in the formation of a linear trinuclear complex, [Cu2Na(L·SMe)4]NO3·3MeOH (5), characterized by antiferromagnetic exchange interactions between the two copper ions.American Chemical Society2019201920182019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion12 p.application/pdfhttps://hdl.handle.net/2445/143967Articles publicats en revistes (Química Inorgànica i Orgànica)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.8b01279Inorganic Chemistry, 2018, vol. 57, num. 15, p. 9274-9285https://doi.org/10.1021/acs.inorgchem.8b01279(c) American Chemical Society , 2018info:eu-repo/semantics/openAccessoai:recercat.cat:2445/1439672026-05-29T05:05:01Z
dc.title.none.fl_str_mv Element-Selective Molecular Charge Transport Characteristics of Binuclear Copper(II)-Lanthanide(III) Complexes
title Element-Selective Molecular Charge Transport Characteristics of Binuclear Copper(II)-Lanthanide(III) Complexes
spellingShingle Element-Selective Molecular Charge Transport Characteristics of Binuclear Copper(II)-Lanthanide(III) Complexes
Schmitz, Sebastian
Ions
Compostos complexos
Ions
Complex compounds
title_short Element-Selective Molecular Charge Transport Characteristics of Binuclear Copper(II)-Lanthanide(III) Complexes
title_full Element-Selective Molecular Charge Transport Characteristics of Binuclear Copper(II)-Lanthanide(III) Complexes
title_fullStr Element-Selective Molecular Charge Transport Characteristics of Binuclear Copper(II)-Lanthanide(III) Complexes
title_full_unstemmed Element-Selective Molecular Charge Transport Characteristics of Binuclear Copper(II)-Lanthanide(III) Complexes
title_sort Element-Selective Molecular Charge Transport Characteristics of Binuclear Copper(II)-Lanthanide(III) Complexes
dc.creator.none.fl_str_mv Schmitz, Sebastian
Kovalchuk, Andrew
Martín Rodríguez, Alejandro
van Leusen, Jan
Izarova, Natalya V.
Bourone, Svenja D. M.
Ai, Yong
Ruiz Sabín, Eliseo
Chiechi, Ryan C.
Kögerler, Paul
Monakhov, Kirill Yu.
author Schmitz, Sebastian
author_facet Schmitz, Sebastian
Kovalchuk, Andrew
Martín Rodríguez, Alejandro
van Leusen, Jan
Izarova, Natalya V.
Bourone, Svenja D. M.
Ai, Yong
Ruiz Sabín, Eliseo
Chiechi, Ryan C.
Kögerler, Paul
Monakhov, Kirill Yu.
author_role author
author2 Kovalchuk, Andrew
Martín Rodríguez, Alejandro
van Leusen, Jan
Izarova, Natalya V.
Bourone, Svenja D. M.
Ai, Yong
Ruiz Sabín, Eliseo
Chiechi, Ryan C.
Kögerler, Paul
Monakhov, Kirill Yu.
author2_role author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Ions
Compostos complexos
Ions
Complex compounds
topic Ions
Compostos complexos
Ions
Complex compounds
description A series of isostructural dinuclear 3d-4f complexes, isolated as [CuLn(L·SMe)2(OOCMe)2(NO3)]·xMeOH (Ln = Gd 1, Tb 2, Dy 3, and Y 4; x = 0.75-1) and comprising one acetate and two thioether-Schiff base (L·SMe-) bridging ligands based on 4-(methylthio)aniline and 2-hydroxy-3-methoxybenzaldehyde (HL·SMe = C15H15NO2S), was synthesized and fully characterized. The magnetic properties of the charge-neutral {CuLn} complexes are dominated by ferromagnetic CuII-LnIII exchange interactions. Large-area electron transport studies reveal that the average conductivity of robust, self-assembled {CuLn} monolayers on a gold substrate is significantly lower than that of common alkanethiolates. Theoretical calculations of transmission spectra of individual complexes 1 and 4 embedded between two metallic electrodes show that the molecular current-voltage (I-V) characteristics are strongly influenced by electron transport through the Cu centers and thus fully independent of the lanthanide ion, in excellent agreement with the experimental I-V data for 1-4. The β-polarized transmission indicated by calculations of 1 and 4 points out their potential as spin filters. In addition, the reactivity of the title compound 1 with CuII in a square-pyramidal coordination environment toward methanolate and azide was examined, resulting in the formation of a linear trinuclear complex, [Cu2Na(L·SMe)4]NO3·3MeOH (5), characterized by antiferromagnetic exchange interactions between the two copper ions.
publishDate 2018
dc.date.none.fl_str_mv 2018
2019
2019
2019
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/2445/143967
url https://hdl.handle.net/2445/143967
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.8b01279
Inorganic Chemistry, 2018, vol. 57, num. 15, p. 9274-9285
https://doi.org/10.1021/acs.inorgchem.8b01279
dc.rights.none.fl_str_mv (c) American Chemical Society , 2018
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) American Chemical Society , 2018
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 12 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 (Química Inorgànica i Orgànica)
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
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score 15.811543