Copper complexes with new oxaaza-pendant-armed macrocyclic ligands: X-ray crystal structure of a macrocyclic copper(II) complex

Detalhes bibliográficos
Autor(a) principal: Vicente, Manuel
Data de Publicação: 2005
Outros Autores: Bastida, Rufina, Macías, Alejandro, Valencia, Laura, Geraldes, Carlos F. G. C., Brondino, Carlos D.
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10316/3865
https://doi.org/10.1016/j.ica.2004.11.006
Resumo: The synthesis of new oxaaza macrocyclic ligands (2-4) derived from O1,O7-bis(2-formylphenyl)-1,4,7-trioxaheptane and functionalized tris(2-aminoethyl)amine are described. Mononuclear copper(II) complexes were isolated in the reaction of the corresponding macrocyclic ligand and copper(II) perchlorate. The structure of the [Cu(2)](ClO4)2 complex was determined by X-ray diffraction analysis. The copper(II) ion is five-coordinated by all N5 donor atoms, efficiently encapsulated by the amine terminal pendant-arm, with a trigonal-bipyramidal geometry. The complexes are further characterized by UV-Vis, IR and EPR studies. The electronic reflectance spectra evidence that the coordination geometry for the Cu(II) complexes is trigonal-bipyramidal with the ligands 1 and 2 or distorted square-pyramidal with the ligands 3 and 4. The electronic spectra in MeCN solutions are different from those in the solid state, which suggest that some structural modification may occur in solution. The EPR spectrum of powder samples of the copper complex with 2 presents axial symmetry with hyperfine split at g// with the copper nuclei (I = 3/2), which is characteristic of weakly exchange coupled extended systems. The EPR parameters (g// = 2.230, A// = 156 × 10-4 cm-1 and g[perpendicular] = 2.085) indicate a dx2-y2 ground state. The EPR spectra of the complexes with ligands 3and 4 show EPR spectra with a poorly resolved hyperfine structure at g//. In contrast, the complex with ligand 2 shows no hyperfine split and a line shape which was simulated assuming rhombic g-tensor (g1 = 2.030, g2 = 2.115 and g3 = 2.190).
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spelling Copper complexes with new oxaaza-pendant-armed macrocyclic ligands: X-ray crystal structure of a macrocyclic copper(II) complexCopper(II) complexOxaaza macrocycleTris(2-aminoethyl)amineCrystal structure, EPRThe synthesis of new oxaaza macrocyclic ligands (2-4) derived from O1,O7-bis(2-formylphenyl)-1,4,7-trioxaheptane and functionalized tris(2-aminoethyl)amine are described. Mononuclear copper(II) complexes were isolated in the reaction of the corresponding macrocyclic ligand and copper(II) perchlorate. The structure of the [Cu(2)](ClO4)2 complex was determined by X-ray diffraction analysis. The copper(II) ion is five-coordinated by all N5 donor atoms, efficiently encapsulated by the amine terminal pendant-arm, with a trigonal-bipyramidal geometry. The complexes are further characterized by UV-Vis, IR and EPR studies. The electronic reflectance spectra evidence that the coordination geometry for the Cu(II) complexes is trigonal-bipyramidal with the ligands 1 and 2 or distorted square-pyramidal with the ligands 3 and 4. The electronic spectra in MeCN solutions are different from those in the solid state, which suggest that some structural modification may occur in solution. The EPR spectrum of powder samples of the copper complex with 2 presents axial symmetry with hyperfine split at g// with the copper nuclei (I = 3/2), which is characteristic of weakly exchange coupled extended systems. The EPR parameters (g// = 2.230, A// = 156 × 10-4 cm-1 and g[perpendicular] = 2.085) indicate a dx2-y2 ground state. The EPR spectra of the complexes with ligands 3and 4 show EPR spectra with a poorly resolved hyperfine structure at g//. In contrast, the complex with ligand 2 shows no hyperfine split and a line shape which was simulated assuming rhombic g-tensor (g1 = 2.030, g2 = 2.115 and g3 = 2.190).http://www.sciencedirect.com/science/article/B6TG5-4F02M3R-B/1/9fb378e69c125e05e7458b03422aeec62005info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleaplication/PDFhttp://hdl.handle.net/10316/3865http://hdl.handle.net/10316/3865https://doi.org/10.1016/j.ica.2004.11.006engInorganica Chimica Acta. 358:4 (2005) 1141-1150Vicente, ManuelBastida, RufinaMacías, AlejandroValencia, LauraGeraldes, Carlos F. G. C.Brondino, Carlos D.info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2020-11-06T16:49:07Zoai:estudogeral.uc.pt:10316/3865Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:55:46.210157Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse
dc.title.none.fl_str_mv Copper complexes with new oxaaza-pendant-armed macrocyclic ligands: X-ray crystal structure of a macrocyclic copper(II) complex
title Copper complexes with new oxaaza-pendant-armed macrocyclic ligands: X-ray crystal structure of a macrocyclic copper(II) complex
spellingShingle Copper complexes with new oxaaza-pendant-armed macrocyclic ligands: X-ray crystal structure of a macrocyclic copper(II) complex
Vicente, Manuel
Copper(II) complex
Oxaaza macrocycle
Tris(2-aminoethyl)amine
Crystal structure, EPR
title_short Copper complexes with new oxaaza-pendant-armed macrocyclic ligands: X-ray crystal structure of a macrocyclic copper(II) complex
title_full Copper complexes with new oxaaza-pendant-armed macrocyclic ligands: X-ray crystal structure of a macrocyclic copper(II) complex
title_fullStr Copper complexes with new oxaaza-pendant-armed macrocyclic ligands: X-ray crystal structure of a macrocyclic copper(II) complex
title_full_unstemmed Copper complexes with new oxaaza-pendant-armed macrocyclic ligands: X-ray crystal structure of a macrocyclic copper(II) complex
title_sort Copper complexes with new oxaaza-pendant-armed macrocyclic ligands: X-ray crystal structure of a macrocyclic copper(II) complex
author Vicente, Manuel
author_facet Vicente, Manuel
Bastida, Rufina
Macías, Alejandro
Valencia, Laura
Geraldes, Carlos F. G. C.
Brondino, Carlos D.
author_role author
author2 Bastida, Rufina
Macías, Alejandro
Valencia, Laura
Geraldes, Carlos F. G. C.
Brondino, Carlos D.
author2_role author
author
author
author
author
dc.contributor.author.fl_str_mv Vicente, Manuel
Bastida, Rufina
Macías, Alejandro
Valencia, Laura
Geraldes, Carlos F. G. C.
Brondino, Carlos D.
dc.subject.por.fl_str_mv Copper(II) complex
Oxaaza macrocycle
Tris(2-aminoethyl)amine
Crystal structure, EPR
topic Copper(II) complex
Oxaaza macrocycle
Tris(2-aminoethyl)amine
Crystal structure, EPR
description The synthesis of new oxaaza macrocyclic ligands (2-4) derived from O1,O7-bis(2-formylphenyl)-1,4,7-trioxaheptane and functionalized tris(2-aminoethyl)amine are described. Mononuclear copper(II) complexes were isolated in the reaction of the corresponding macrocyclic ligand and copper(II) perchlorate. The structure of the [Cu(2)](ClO4)2 complex was determined by X-ray diffraction analysis. The copper(II) ion is five-coordinated by all N5 donor atoms, efficiently encapsulated by the amine terminal pendant-arm, with a trigonal-bipyramidal geometry. The complexes are further characterized by UV-Vis, IR and EPR studies. The electronic reflectance spectra evidence that the coordination geometry for the Cu(II) complexes is trigonal-bipyramidal with the ligands 1 and 2 or distorted square-pyramidal with the ligands 3 and 4. The electronic spectra in MeCN solutions are different from those in the solid state, which suggest that some structural modification may occur in solution. The EPR spectrum of powder samples of the copper complex with 2 presents axial symmetry with hyperfine split at g// with the copper nuclei (I = 3/2), which is characteristic of weakly exchange coupled extended systems. The EPR parameters (g// = 2.230, A// = 156 × 10-4 cm-1 and g[perpendicular] = 2.085) indicate a dx2-y2 ground state. The EPR spectra of the complexes with ligands 3and 4 show EPR spectra with a poorly resolved hyperfine structure at g//. In contrast, the complex with ligand 2 shows no hyperfine split and a line shape which was simulated assuming rhombic g-tensor (g1 = 2.030, g2 = 2.115 and g3 = 2.190).
publishDate 2005
dc.date.none.fl_str_mv 2005
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
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status_str publishedVersion
dc.identifier.uri.fl_str_mv http://hdl.handle.net/10316/3865
http://hdl.handle.net/10316/3865
https://doi.org/10.1016/j.ica.2004.11.006
url http://hdl.handle.net/10316/3865
https://doi.org/10.1016/j.ica.2004.11.006
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv Inorganica Chimica Acta. 358:4 (2005) 1141-1150
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dc.format.none.fl_str_mv aplication/PDF
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