Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes
- Autores
- Cáceres Vázquez, Joaquín; Jara, Danilo H.; Costamagna, Juan; Martínez Gómez, Fabián; Silva, Carlos; Lemus, Luis; Freire Espeleta, Eleonora; Baggio, Ricardo Fortunato; Vera, Cristian; Guerrero, Juan
- Año de publicación
- 2022
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- A series of six new Cu(i) complexes with ([Cu(N-{4-R}pyridine-2-yl-methanimine)(PPh3)Br]) formulation, where R corresponds to a donor or acceptor p-substituent, have been synthesized and were used to study self-association effects on their structural and electrochemical properties. X-ray diffraction results showed that in all complexes the packing is organized from a dimer generated by supramolecular π stacking and hydrogen bonding. 1H-NMR experiments at several concentrations showed that all complexes undergo a fast-self-association monomer-dimer equilibrium in solution, while changes in resonance frequency towards the high or low field in specific protons of the imine ligand allow establishing that dimers have similar structures to those found in the crystal. The thermodynamic parameters for this self-association process were calculated from dimerization constants determined by VT-1H-NMR experiments for several concentrations at different temperatures. The values for KD (4.0 to 70.0 M−1 range), ΔH (−1.4 to −2.6 kcal mol−1 range), ΔS (−0.2 to 2.1 cal mol−1 K−1 range), and ΔG298 (−0.8 to −2.0 kcal mol−1 range) are of the same order and indicate that the self-dimerization process is enthalpically driven for all complexes. The electrochemical profile of the complexes shows two redox Cu(ii)/Cu(i) processes whose relative intensities are sensitive to concentration changes, indicating that both species are in chemical equilibrium, with the monomer and the dimer having different electrochemical characteristics. We associate this behaviour with the structural lability of the Cu(i) centre that allows the monomeric molecules to reorder conformationally to achieve a more adequate assembly in the non-covalent dimer. As expected, structural properties in the solid and in solution, as well as their electrochemical properties, are not correlated with the electronic parameters usually used to evaluate R substituent effects. This confirms that the properties of the Cu(i) complexes are usually more influenced by steric effects than by the inductive effects of substituents of the ligands. In fact, the results obtained showed the importance of non-covalent intermolecular interactions in the structuring of the coordination geometry around the Cu centre and in the coordinative stability to avoid dissociative equilibria.
Fil: Cáceres Vázquez, Joaquín. Universidad de Santiago de Chile; Chile
Fil: Jara, Danilo H.. Universidad Adolfo Ibañez; Chile
Fil: Costamagna, Juan. Universidad de Santiago de Chile; Chile
Fil: Martínez Gómez, Fabián. Universidad de Santiago de Chile; Chile
Fil: Silva, Carlos. Universidad de Santiago de Chile; Chile
Fil: Lemus, Luis. Universidad de Santiago de Chile; Chile
Fil: Freire Espeleta, Eleonora. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina
Fil: Vera, Cristian. Universidad de Santiago de Chile; Chile
Fil: Guerrero, Juan. Universidad de Santiago de Chile; Chile - Materia
-
Cu complexes
Cristal structure - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/202670
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Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexesCáceres Vázquez, JoaquínJara, Danilo H.Costamagna, JuanMartínez Gómez, FabiánSilva, CarlosLemus, LuisFreire Espeleta, EleonoraBaggio, Ricardo FortunatoVera, CristianGuerrero, JuanCu complexesCristal structurehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A series of six new Cu(i) complexes with ([Cu(N-{4-R}pyridine-2-yl-methanimine)(PPh3)Br]) formulation, where R corresponds to a donor or acceptor p-substituent, have been synthesized and were used to study self-association effects on their structural and electrochemical properties. X-ray diffraction results showed that in all complexes the packing is organized from a dimer generated by supramolecular π stacking and hydrogen bonding. 1H-NMR experiments at several concentrations showed that all complexes undergo a fast-self-association monomer-dimer equilibrium in solution, while changes in resonance frequency towards the high or low field in specific protons of the imine ligand allow establishing that dimers have similar structures to those found in the crystal. The thermodynamic parameters for this self-association process were calculated from dimerization constants determined by VT-1H-NMR experiments for several concentrations at different temperatures. The values for KD (4.0 to 70.0 M−1 range), ΔH (−1.4 to −2.6 kcal mol−1 range), ΔS (−0.2 to 2.1 cal mol−1 K−1 range), and ΔG298 (−0.8 to −2.0 kcal mol−1 range) are of the same order and indicate that the self-dimerization process is enthalpically driven for all complexes. The electrochemical profile of the complexes shows two redox Cu(ii)/Cu(i) processes whose relative intensities are sensitive to concentration changes, indicating that both species are in chemical equilibrium, with the monomer and the dimer having different electrochemical characteristics. We associate this behaviour with the structural lability of the Cu(i) centre that allows the monomeric molecules to reorder conformationally to achieve a more adequate assembly in the non-covalent dimer. As expected, structural properties in the solid and in solution, as well as their electrochemical properties, are not correlated with the electronic parameters usually used to evaluate R substituent effects. This confirms that the properties of the Cu(i) complexes are usually more influenced by steric effects than by the inductive effects of substituents of the ligands. In fact, the results obtained showed the importance of non-covalent intermolecular interactions in the structuring of the coordination geometry around the Cu centre and in the coordinative stability to avoid dissociative equilibria.Fil: Cáceres Vázquez, Joaquín. Universidad de Santiago de Chile; ChileFil: Jara, Danilo H.. Universidad Adolfo Ibañez; ChileFil: Costamagna, Juan. Universidad de Santiago de Chile; ChileFil: Martínez Gómez, Fabián. Universidad de Santiago de Chile; ChileFil: Silva, Carlos. Universidad de Santiago de Chile; ChileFil: Lemus, Luis. Universidad de Santiago de Chile; ChileFil: Freire Espeleta, Eleonora. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; ArgentinaFil: Vera, Cristian. Universidad de Santiago de Chile; ChileFil: Guerrero, Juan. Universidad de Santiago de Chile; ChileRoyal Society of Chemistry2022-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/202670Cáceres Vázquez, Joaquín; Jara, Danilo H.; Costamagna, Juan; Martínez Gómez, Fabián; Silva, Carlos; et al.; Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes; Royal Society of Chemistry; RSC Advances; 13; 2; 12-2022; 825-8382046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/d2ra05341ainfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:47:45Zoai:ri.conicet.gov.ar:11336/202670instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:47:46.043CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes |
title |
Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes |
spellingShingle |
Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes Cáceres Vázquez, Joaquín Cu complexes Cristal structure |
title_short |
Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes |
title_full |
Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes |
title_fullStr |
Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes |
title_full_unstemmed |
Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes |
title_sort |
Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes |
dc.creator.none.fl_str_mv |
Cáceres Vázquez, Joaquín Jara, Danilo H. Costamagna, Juan Martínez Gómez, Fabián Silva, Carlos Lemus, Luis Freire Espeleta, Eleonora Baggio, Ricardo Fortunato Vera, Cristian Guerrero, Juan |
author |
Cáceres Vázquez, Joaquín |
author_facet |
Cáceres Vázquez, Joaquín Jara, Danilo H. Costamagna, Juan Martínez Gómez, Fabián Silva, Carlos Lemus, Luis Freire Espeleta, Eleonora Baggio, Ricardo Fortunato Vera, Cristian Guerrero, Juan |
author_role |
author |
author2 |
Jara, Danilo H. Costamagna, Juan Martínez Gómez, Fabián Silva, Carlos Lemus, Luis Freire Espeleta, Eleonora Baggio, Ricardo Fortunato Vera, Cristian Guerrero, Juan |
author2_role |
author author author author author author author author author |
dc.subject.none.fl_str_mv |
Cu complexes Cristal structure |
topic |
Cu complexes Cristal structure |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
A series of six new Cu(i) complexes with ([Cu(N-{4-R}pyridine-2-yl-methanimine)(PPh3)Br]) formulation, where R corresponds to a donor or acceptor p-substituent, have been synthesized and were used to study self-association effects on their structural and electrochemical properties. X-ray diffraction results showed that in all complexes the packing is organized from a dimer generated by supramolecular π stacking and hydrogen bonding. 1H-NMR experiments at several concentrations showed that all complexes undergo a fast-self-association monomer-dimer equilibrium in solution, while changes in resonance frequency towards the high or low field in specific protons of the imine ligand allow establishing that dimers have similar structures to those found in the crystal. The thermodynamic parameters for this self-association process were calculated from dimerization constants determined by VT-1H-NMR experiments for several concentrations at different temperatures. The values for KD (4.0 to 70.0 M−1 range), ΔH (−1.4 to −2.6 kcal mol−1 range), ΔS (−0.2 to 2.1 cal mol−1 K−1 range), and ΔG298 (−0.8 to −2.0 kcal mol−1 range) are of the same order and indicate that the self-dimerization process is enthalpically driven for all complexes. The electrochemical profile of the complexes shows two redox Cu(ii)/Cu(i) processes whose relative intensities are sensitive to concentration changes, indicating that both species are in chemical equilibrium, with the monomer and the dimer having different electrochemical characteristics. We associate this behaviour with the structural lability of the Cu(i) centre that allows the monomeric molecules to reorder conformationally to achieve a more adequate assembly in the non-covalent dimer. As expected, structural properties in the solid and in solution, as well as their electrochemical properties, are not correlated with the electronic parameters usually used to evaluate R substituent effects. This confirms that the properties of the Cu(i) complexes are usually more influenced by steric effects than by the inductive effects of substituents of the ligands. In fact, the results obtained showed the importance of non-covalent intermolecular interactions in the structuring of the coordination geometry around the Cu centre and in the coordinative stability to avoid dissociative equilibria. Fil: Cáceres Vázquez, Joaquín. Universidad de Santiago de Chile; Chile Fil: Jara, Danilo H.. Universidad Adolfo Ibañez; Chile Fil: Costamagna, Juan. Universidad de Santiago de Chile; Chile Fil: Martínez Gómez, Fabián. Universidad de Santiago de Chile; Chile Fil: Silva, Carlos. Universidad de Santiago de Chile; Chile Fil: Lemus, Luis. Universidad de Santiago de Chile; Chile Fil: Freire Espeleta, Eleonora. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Universidad Nacional de San Martín; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina Fil: Vera, Cristian. Universidad de Santiago de Chile; Chile Fil: Guerrero, Juan. Universidad de Santiago de Chile; Chile |
description |
A series of six new Cu(i) complexes with ([Cu(N-{4-R}pyridine-2-yl-methanimine)(PPh3)Br]) formulation, where R corresponds to a donor or acceptor p-substituent, have been synthesized and were used to study self-association effects on their structural and electrochemical properties. X-ray diffraction results showed that in all complexes the packing is organized from a dimer generated by supramolecular π stacking and hydrogen bonding. 1H-NMR experiments at several concentrations showed that all complexes undergo a fast-self-association monomer-dimer equilibrium in solution, while changes in resonance frequency towards the high or low field in specific protons of the imine ligand allow establishing that dimers have similar structures to those found in the crystal. The thermodynamic parameters for this self-association process were calculated from dimerization constants determined by VT-1H-NMR experiments for several concentrations at different temperatures. The values for KD (4.0 to 70.0 M−1 range), ΔH (−1.4 to −2.6 kcal mol−1 range), ΔS (−0.2 to 2.1 cal mol−1 K−1 range), and ΔG298 (−0.8 to −2.0 kcal mol−1 range) are of the same order and indicate that the self-dimerization process is enthalpically driven for all complexes. The electrochemical profile of the complexes shows two redox Cu(ii)/Cu(i) processes whose relative intensities are sensitive to concentration changes, indicating that both species are in chemical equilibrium, with the monomer and the dimer having different electrochemical characteristics. We associate this behaviour with the structural lability of the Cu(i) centre that allows the monomeric molecules to reorder conformationally to achieve a more adequate assembly in the non-covalent dimer. As expected, structural properties in the solid and in solution, as well as their electrochemical properties, are not correlated with the electronic parameters usually used to evaluate R substituent effects. This confirms that the properties of the Cu(i) complexes are usually more influenced by steric effects than by the inductive effects of substituents of the ligands. In fact, the results obtained showed the importance of non-covalent intermolecular interactions in the structuring of the coordination geometry around the Cu centre and in the coordinative stability to avoid dissociative equilibria. |
publishDate |
2022 |
dc.date.none.fl_str_mv |
2022-12 |
dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
format |
article |
status_str |
publishedVersion |
dc.identifier.none.fl_str_mv |
http://hdl.handle.net/11336/202670 Cáceres Vázquez, Joaquín; Jara, Danilo H.; Costamagna, Juan; Martínez Gómez, Fabián; Silva, Carlos; et al.; Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes; Royal Society of Chemistry; RSC Advances; 13; 2; 12-2022; 825-838 2046-2069 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/202670 |
identifier_str_mv |
Cáceres Vázquez, Joaquín; Jara, Danilo H.; Costamagna, Juan; Martínez Gómez, Fabián; Silva, Carlos; et al.; Effect of non-covalent self-dimerization on the spectroscopic and electrochemical properties of mixed Cu(i) complexes; Royal Society of Chemistry; RSC Advances; 13; 2; 12-2022; 825-838 2046-2069 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/doi/10.1039/d2ra05341a |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by-nc/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf 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 |
reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
reponame_str |
CONICET Digital (CONICET) |
collection |
CONICET Digital (CONICET) |
instname_str |
Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.name.fl_str_mv |
CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.mail.fl_str_mv |
dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
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1844613487103311872 |
score |
13.070432 |