Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complex

Autores
Santa Maria de la Parra, Lucía; Riafrecha, Leonardo Ezequiel; Echeverría, Gustavo Alberto; Lezama, Luis; Piro, Oscar Enrique; Gil, Diego Mauricio; Frontera, Antonio; Leon, Ignacio Esteban
Año de publicación
2025
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
This study details the synthesis of a novel ligand, (E)-5-chloro-N´-(2-hydroxy-3-methoxybenzylidene) thiophene-2-carbohydrazide ligand (for short, H2L), and its tetranuclear Cu(II) complex (Cu4L4), together with their X-ray crystal structures and the magnetic properties and EPR spectra of Cu4L4 within 4-300K temperature range. Furthermore, we report the spectroscopic characterization (FTIR and UV-Vis) of the compounds and perform a Hirshfeld analysis of their non-covalent interactions, along with certain quantum chemical calculations. H2L crystallizes in the monoclinic space group Cc with Z = 8 molecules per unit cell, and Cu4L4 complex in the tetragonal space group P41/a with Z = 4. The complex is at a crystal site of S4 symmetry, conforming to a cubane-like Cu4O4 core. The main path for exchange interaction between neighboring copper ions in the core involves a relatively large overlap of copper d(x2-y2) electron ground state orbital with the sp2 lone-pair lobes of the bridging oxygen. Magnetic susceptibility in the 5-300 K range, mainly interpreted with the exchange Hamiltonian confirms the expected relatively strong antiferromagnetic (AF) character of the complex (J = -61.5(1) cm-1). The powder room temperature Q-band EPR spectrum shows a very broad band (ΔBpp = 1980 Gauss) corresponding to a gyromagnetic g-factor of 2.13. The band intensity decreases sharply with temperature, as expected for a Cu(II) tetramer with a well isolated spin singlet (S = 0) ground state.
Fil: Santa Maria de la Parra, Lucía. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Riafrecha, Leonardo Ezequiel. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina
Fil: Echeverría, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina
Fil: Lezama, Luis. Universidad del País Vasco; España
Fil: Piro, Oscar Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina
Fil: Gil, Diego Mauricio. Universidad Nacional de Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria; Argentina
Fil: Frontera, Antonio. Universidad de las Islas Baleares; España
Fil: Leon, Ignacio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Materia
Complex
Hydrazone
Copper
Crystal
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/280729
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/280729
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complexSanta Maria de la Parra, LucíaRiafrecha, Leonardo EzequielEcheverría, Gustavo AlbertoLezama, LuisPiro, Oscar EnriqueGil, Diego MauricioFrontera, AntonioLeon, Ignacio EstebanComplexHydrazoneCopperCrystalhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1This study details the synthesis of a novel ligand, (E)-5-chloro-N´-(2-hydroxy-3-methoxybenzylidene) thiophene-2-carbohydrazide ligand (for short, H2L), and its tetranuclear Cu(II) complex (Cu4L4), together with their X-ray crystal structures and the magnetic properties and EPR spectra of Cu4L4 within 4-300K temperature range. Furthermore, we report the spectroscopic characterization (FTIR and UV-Vis) of the compounds and perform a Hirshfeld analysis of their non-covalent interactions, along with certain quantum chemical calculations. H2L crystallizes in the monoclinic space group Cc with Z = 8 molecules per unit cell, and Cu4L4 complex in the tetragonal space group P41/a with Z = 4. The complex is at a crystal site of S4 symmetry, conforming to a cubane-like Cu4O4 core. The main path for exchange interaction between neighboring copper ions in the core involves a relatively large overlap of copper d(x2-y2) electron ground state orbital with the sp2 lone-pair lobes of the bridging oxygen. Magnetic susceptibility in the 5-300 K range, mainly interpreted with the exchange Hamiltonian confirms the expected relatively strong antiferromagnetic (AF) character of the complex (J = -61.5(1) cm-1). The powder room temperature Q-band EPR spectrum shows a very broad band (ΔBpp = 1980 Gauss) corresponding to a gyromagnetic g-factor of 2.13. The band intensity decreases sharply with temperature, as expected for a Cu(II) tetramer with a well isolated spin singlet (S = 0) ground state.Fil: Santa Maria de la Parra, Lucía. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Riafrecha, Leonardo Ezequiel. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; ArgentinaFil: Echeverría, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; ArgentinaFil: Lezama, Luis. Universidad del País Vasco; EspañaFil: Piro, Oscar Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; ArgentinaFil: Gil, Diego Mauricio. Universidad Nacional de Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria; ArgentinaFil: Frontera, Antonio. Universidad de las Islas Baleares; EspañaFil: Leon, Ignacio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaRoyal Society of Chemistry2025-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/280729Santa Maria de la Parra, Lucía; Riafrecha, Leonardo Ezequiel; Echeverría, Gustavo Alberto; Lezama, Luis; Piro, Oscar Enrique; et al.; Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complex; Royal Society of Chemistry; Dalton Transactions; 54; 37; 8-2025; 13976-139891477-9226CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2025/DT/D5DT01463Hinfo:eu-repo/semantics/altIdentifier/doi/10.1039/D5DT01463Hinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-02-06T13:26:13Zoai:ri.conicet.gov.ar:11336/280729instacron: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:34982026-02-06 13:26:13.819CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complex
title Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complex
spellingShingle Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complex
Santa Maria de la Parra, Lucía
Complex
Hydrazone
Copper
Crystal
title_short Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complex
title_full Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complex
title_fullStr Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complex
title_full_unstemmed Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complex
title_sort Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complex
dc.creator.none.fl_str_mv Santa Maria de la Parra, Lucía
Riafrecha, Leonardo Ezequiel
Echeverría, Gustavo Alberto
Lezama, Luis
Piro, Oscar Enrique
Gil, Diego Mauricio
Frontera, Antonio
Leon, Ignacio Esteban
author Santa Maria de la Parra, Lucía
author_facet Santa Maria de la Parra, Lucía
Riafrecha, Leonardo Ezequiel
Echeverría, Gustavo Alberto
Lezama, Luis
Piro, Oscar Enrique
Gil, Diego Mauricio
Frontera, Antonio
Leon, Ignacio Esteban
author_role author
author2 Riafrecha, Leonardo Ezequiel
Echeverría, Gustavo Alberto
Lezama, Luis
Piro, Oscar Enrique
Gil, Diego Mauricio
Frontera, Antonio
Leon, Ignacio Esteban
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Complex
Hydrazone
Copper
Crystal
topic Complex
Hydrazone
Copper
Crystal
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv This study details the synthesis of a novel ligand, (E)-5-chloro-N´-(2-hydroxy-3-methoxybenzylidene) thiophene-2-carbohydrazide ligand (for short, H2L), and its tetranuclear Cu(II) complex (Cu4L4), together with their X-ray crystal structures and the magnetic properties and EPR spectra of Cu4L4 within 4-300K temperature range. Furthermore, we report the spectroscopic characterization (FTIR and UV-Vis) of the compounds and perform a Hirshfeld analysis of their non-covalent interactions, along with certain quantum chemical calculations. H2L crystallizes in the monoclinic space group Cc with Z = 8 molecules per unit cell, and Cu4L4 complex in the tetragonal space group P41/a with Z = 4. The complex is at a crystal site of S4 symmetry, conforming to a cubane-like Cu4O4 core. The main path for exchange interaction between neighboring copper ions in the core involves a relatively large overlap of copper d(x2-y2) electron ground state orbital with the sp2 lone-pair lobes of the bridging oxygen. Magnetic susceptibility in the 5-300 K range, mainly interpreted with the exchange Hamiltonian confirms the expected relatively strong antiferromagnetic (AF) character of the complex (J = -61.5(1) cm-1). The powder room temperature Q-band EPR spectrum shows a very broad band (ΔBpp = 1980 Gauss) corresponding to a gyromagnetic g-factor of 2.13. The band intensity decreases sharply with temperature, as expected for a Cu(II) tetramer with a well isolated spin singlet (S = 0) ground state.
Fil: Santa Maria de la Parra, Lucía. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Riafrecha, Leonardo Ezequiel. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Estudio de Compuestos Orgánicos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina
Fil: Echeverría, Gustavo Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina
Fil: Lezama, Luis. Universidad del País Vasco; España
Fil: Piro, Oscar Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Física La Plata. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Física La Plata; Argentina
Fil: Gil, Diego Mauricio. Universidad Nacional de Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria; Argentina
Fil: Frontera, Antonio. Universidad de las Islas Baleares; España
Fil: Leon, Ignacio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
description This study details the synthesis of a novel ligand, (E)-5-chloro-N´-(2-hydroxy-3-methoxybenzylidene) thiophene-2-carbohydrazide ligand (for short, H2L), and its tetranuclear Cu(II) complex (Cu4L4), together with their X-ray crystal structures and the magnetic properties and EPR spectra of Cu4L4 within 4-300K temperature range. Furthermore, we report the spectroscopic characterization (FTIR and UV-Vis) of the compounds and perform a Hirshfeld analysis of their non-covalent interactions, along with certain quantum chemical calculations. H2L crystallizes in the monoclinic space group Cc with Z = 8 molecules per unit cell, and Cu4L4 complex in the tetragonal space group P41/a with Z = 4. The complex is at a crystal site of S4 symmetry, conforming to a cubane-like Cu4O4 core. The main path for exchange interaction between neighboring copper ions in the core involves a relatively large overlap of copper d(x2-y2) electron ground state orbital with the sp2 lone-pair lobes of the bridging oxygen. Magnetic susceptibility in the 5-300 K range, mainly interpreted with the exchange Hamiltonian confirms the expected relatively strong antiferromagnetic (AF) character of the complex (J = -61.5(1) cm-1). The powder room temperature Q-band EPR spectrum shows a very broad band (ΔBpp = 1980 Gauss) corresponding to a gyromagnetic g-factor of 2.13. The band intensity decreases sharply with temperature, as expected for a Cu(II) tetramer with a well isolated spin singlet (S = 0) ground state.
publishDate 2025
dc.date.none.fl_str_mv 2025-08
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/11336/280729
Santa Maria de la Parra, Lucía; Riafrecha, Leonardo Ezequiel; Echeverría, Gustavo Alberto; Lezama, Luis; Piro, Oscar Enrique; et al.; Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complex; Royal Society of Chemistry; Dalton Transactions; 54; 37; 8-2025; 13976-13989
1477-9226
CONICET Digital
CONICET
url http://hdl.handle.net/11336/280729
identifier_str_mv Santa Maria de la Parra, Lucía; Riafrecha, Leonardo Ezequiel; Echeverría, Gustavo Alberto; Lezama, Luis; Piro, Oscar Enrique; et al.; Structural, spectroscopic, theoretical, and magnetic investigations of a novel cubane-like tetranuclear copper( ii )-hydrazone complex; Royal Society of Chemistry; Dalton Transactions; 54; 37; 8-2025; 13976-13989
1477-9226
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2025/DT/D5DT01463H
info:eu-repo/semantics/altIdentifier/doi/10.1039/D5DT01463H
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
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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score 13.106097

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