Ligand Contributions to the Electronic ...
Type de document :
Article dans une revue scientifique
DOI :
URL permanente :
Titre :
Ligand Contributions to the Electronic Structures of the Oxidized Cobalt(II) salen Complexes
Auteur(s) :
Kochem, Amélie [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Kanso, Hussein [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Baptiste, Benoit [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Arora, Himanshu [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Philouze, Christian [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Jarjayes, Olivier [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Vezin, Herve [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516
Luneau, Dominique [Auteur]
Laboratoire des Multimatériaux et Interfaces [LMI]
Orio, Maylis [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516
Thomas, Fabrice [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Kanso, Hussein [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Baptiste, Benoit [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Arora, Himanshu [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Philouze, Christian [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Jarjayes, Olivier [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Vezin, Herve [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516
Luneau, Dominique [Auteur]
Laboratoire des Multimatériaux et Interfaces [LMI]
Orio, Maylis [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516
Thomas, Fabrice [Auteur]
Département de Chimie Moléculaire - Chimie Inorganique Redox [DCM - CIRE]
Titre de la revue :
INORGANIC CHEMISTRY
Nom court de la revue :
Inorg. Chem.
Numéro :
51
Pagination :
10557-10571
Éditeur :
American Chemical Society (ACS)
Date de publication :
2012-09-26
ISSN :
1520-510X
Mot(s)-clé(s) en anglais :
Oxidation
Quantum mechanics
Metals
Ligands
Ions
Quantum mechanics
Metals
Ligands
Ions
Discipline(s) HAL :
Chimie/Chimie théorique et/ou physique
Résumé en anglais : [en]
Square planar cobalt(II) complexes of salen ligands N,N′-bis(3-tert-butyl-5R-salicylidene)-1,2-cyclohexanediamine), where R = OMe (1) and tert-butyl (2), were prepared. 1 and 2 were electrochemically reversibly oxidized ...
Lire la suite >Square planar cobalt(II) complexes of salen ligands N,N′-bis(3-tert-butyl-5R-salicylidene)-1,2-cyclohexanediamine), where R = OMe (1) and tert-butyl (2), were prepared. 1 and 2 were electrochemically reversibly oxidized into cations [1-H2O]+ and [2-H2O]+ in CH2Cl2. The chemically generated [1-H2O](SbF6)·0.68 H2O·0.82CH2Cl2 and [2-H2O](SbF6)·0.3H2O·0.85CH2Cl2 were characterized by X-ray diffraction and NIR spectroscopy. Both complexes are paramagnetic species containing a square pyramidal cobalt ion coordinated at the apical position by an exogenous water molecule. They exhibit remarkable NIR bands at 1220 (7370 M–1 cm–1) and 1060 nm (5560 M–1 cm–1), respectively, assigned to a CT transition. DFT calculations and magnetic measurements confirm the paramagnetic (S = 1) ground spin state of the cations. They show that more than 70% of the total spin density in [1-H2O]+ and [2-H2O]+ is localized on the metal, the remaining spin density being distributed over the aromatic rings (30% phenoxyl character). In the presence of N-methylimidazole 1 and 2 are irreversibly oxidized by air into the genuine octahedral cobalt(III) bis(phenolate) complexes [1-im2]+ and [2-im2]+, the former being structurally characterized. Neither [1-im2]+ nor [2-im2]+ exhibits a NIR feature in its electronic spectrum. 1 and 2 were electrochemically two-electron oxidized into [1]2+ and [2]2+. The cations were identified as Co(III)–phenoxyl species by their characteristic absorption band at ca. 400 nm in the UV–vis spectrum. Coordination of the phenoxyl radical to the cobalt(III) metal ion is evidenced by the EPR signal centered at g = 2.00.Lire moins >
Lire la suite >Square planar cobalt(II) complexes of salen ligands N,N′-bis(3-tert-butyl-5R-salicylidene)-1,2-cyclohexanediamine), where R = OMe (1) and tert-butyl (2), were prepared. 1 and 2 were electrochemically reversibly oxidized into cations [1-H2O]+ and [2-H2O]+ in CH2Cl2. The chemically generated [1-H2O](SbF6)·0.68 H2O·0.82CH2Cl2 and [2-H2O](SbF6)·0.3H2O·0.85CH2Cl2 were characterized by X-ray diffraction and NIR spectroscopy. Both complexes are paramagnetic species containing a square pyramidal cobalt ion coordinated at the apical position by an exogenous water molecule. They exhibit remarkable NIR bands at 1220 (7370 M–1 cm–1) and 1060 nm (5560 M–1 cm–1), respectively, assigned to a CT transition. DFT calculations and magnetic measurements confirm the paramagnetic (S = 1) ground spin state of the cations. They show that more than 70% of the total spin density in [1-H2O]+ and [2-H2O]+ is localized on the metal, the remaining spin density being distributed over the aromatic rings (30% phenoxyl character). In the presence of N-methylimidazole 1 and 2 are irreversibly oxidized by air into the genuine octahedral cobalt(III) bis(phenolate) complexes [1-im2]+ and [2-im2]+, the former being structurally characterized. Neither [1-im2]+ nor [2-im2]+ exhibits a NIR feature in its electronic spectrum. 1 and 2 were electrochemically two-electron oxidized into [1]2+ and [2]2+. The cations were identified as Co(III)–phenoxyl species by their characteristic absorption band at ca. 400 nm in the UV–vis spectrum. Coordination of the phenoxyl radical to the cobalt(III) metal ion is evidenced by the EPR signal centered at g = 2.00.Lire moins >
Langue :
Anglais
Comité de lecture :
Oui
Audience :
Internationale
Vulgarisation :
Non
Établissement(s) :
Université de Lille
CNRS
CNRS
Collections :
Équipe(s) de recherche :
Propriétés magnéto structurales des matériaux (PMSM)
Date de dépôt :
2021-06-17T15:36:41Z
2021-10-07T13:31:26Z
2021-10-07T13:31:26Z