Tuning the locus of oxidation in ...
Type de document :
Article dans une revue scientifique: Article original
URL permanente :
Titre :
Tuning the locus of oxidation in Cu-diamido-diphenoxo complexes: From Cu(III) to Cu(II)-phenoxyl radical
Auteur(s) :
Eckshtain-Levi, Meital [Auteur]
Bar-Ilan University [Israël]
Lavi, Ronit [Auteur]
Bar-Ilan University [Israël]
Arora, Himanshu [Auteur]
Bar-Ilan University [Israël]
Orio, Maylis [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516
Benisvy, Laurent [Auteur]
Bar-Ilan University [Israël]
Bar-Ilan University [Israël]
Lavi, Ronit [Auteur]
Bar-Ilan University [Israël]
Arora, Himanshu [Auteur]
Bar-Ilan University [Israël]
Orio, Maylis [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516
Benisvy, Laurent [Auteur]
Bar-Ilan University [Israël]
Titre de la revue :
Inorganica Chimica Acta
Numéro :
481
Pagination :
143-150
Date de publication :
2018-09
Discipline(s) HAL :
Chimie/Chimie théorique et/ou physique
Résumé en anglais : [en]
While N2O2 tetraanionic ligands containing a strong N-amidate σ-donor are generally assumed to stabilise metal high valence states, we herein have shown that, in dianionic Cu(II)-diamido-diphenoxo complexes, H-bonding and ...
Lire la suite >While N2O2 tetraanionic ligands containing a strong N-amidate σ-donor are generally assumed to stabilise metal high valence states, we herein have shown that, in dianionic Cu(II)-diamido-diphenoxo complexes, H-bonding and electronic effects on the phenolate groups may modulate the electronic structure of their oxidised species from Cu(III) to Cu(II)-phenoxyl radical complexes; and so in the negative potential range. We observe that electron-poor phenolate complexes 22− and 32− oxidise to Cu(III) species, whereas electron rich phenolate complex 12− oxidises to a Cu(II)-phenoxyl radical. Our DFT results suggest that π-electron-rich phenolate rings in 12− are responsible for an increase of the HOMO orbital energy, bringing the HOMO-SOMO gap small enough to favour a ligand-based oxidation process. Further DFT-calculations have also shown that upon changing the o,p-phenol substituent from electron-widthdrawing groups (NO2) to electron-donating ones (OMe), the favoured oxidised state switches from Cu(III) to Cu(II)-radical. These results emphasize the use of the versatile diamido-diphenoxo backbone as a promising way to novel GO-chemical models, as well as molecular switches.Lire moins >
Lire la suite >While N2O2 tetraanionic ligands containing a strong N-amidate σ-donor are generally assumed to stabilise metal high valence states, we herein have shown that, in dianionic Cu(II)-diamido-diphenoxo complexes, H-bonding and electronic effects on the phenolate groups may modulate the electronic structure of their oxidised species from Cu(III) to Cu(II)-phenoxyl radical complexes; and so in the negative potential range. We observe that electron-poor phenolate complexes 22− and 32− oxidise to Cu(III) species, whereas electron rich phenolate complex 12− oxidises to a Cu(II)-phenoxyl radical. Our DFT results suggest that π-electron-rich phenolate rings in 12− are responsible for an increase of the HOMO orbital energy, bringing the HOMO-SOMO gap small enough to favour a ligand-based oxidation process. Further DFT-calculations have also shown that upon changing the o,p-phenol substituent from electron-widthdrawing groups (NO2) to electron-donating ones (OMe), the favoured oxidised state switches from Cu(III) to Cu(II)-radical. These results emphasize the use of the versatile diamido-diphenoxo backbone as a promising way to novel GO-chemical models, as well as molecular switches.Lire moins >
Langue :
Anglais
Audience :
Internationale
Vulgarisation :
Non
Collections :
Date de dépôt :
2021-11-16T08:23:40Z
2024-02-14T09:35:49Z
2024-02-14T09:35:49Z