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Switching and redox isomerism in first-row transition metal complexes containing redox active Schiff base ligands.

hal.structure.identifierDepartment of Chemistry
dc.contributor.authorSASMAL, Ashok
hal.structure.identifierDepartment of Chemistry
dc.contributor.authorGARRIBBA, Eugenio
hal.structure.identifierInstituto de Ciencia Molecular [ICMol]
dc.contributor.authorGÓMEZ-GARCÍA, Carlos J
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorDESPLANCHES, Cédric
hal.structure.identifierDepartment of Chemistry
dc.contributor.authorMITRA, Samiran
dc.date.issued2014
dc.identifier.issn1477-9226
dc.description.abstractEnThe reversible redox isomerisms in first row transition metal complexes of the type ML2 were studied. The six ML2 complexes (M = Mn(III) (), Fe(II) (), Co(III) (), Ni(II) (), Cu(II) () and Zn(II) ()) were synthesized with a redox active Schiff base ligand [2-(3,5-di-tert-butyl-2-hydroxyphenylamino)-4-chlorophenol] (H3L) presenting different oxidation states from -2 to 0 (L(2-), L(-) and L(0)). EPR spectra and magnetic susceptibility measurements indicate the presence of complexes of the type [Mn(III)(L(2-))(L(-))] () with S = 1/2, [Fe(II)(L(-))2] () with S = 2, [Co(III)(L(2-))(L(-))] () with S = 1/2, [Ni(II)(L(-))2] () with S = 1, [Cu(II)(L(-))2] () with S = 1/2 and [Zn(II)(L(-))2] () with S = 0 at high temperatures. Temperature and solvents influence the electronic structures of the species and give several valence tautomers. At low temperatures these complexes present thermally induced metal-to-ligand (, , ) or ligand-to-ligand (in , ) electron transfer (partial or total), resulting in compounds of the type [Mn(IV)(L(2-))2] () with S = 1/2, [Fe(III)(L(-))(L(2-))] () with S = 1, [Ni(III)(L(2-))(L(-))] () with S = 0, [Cu(II)(L(2-))(L(0))] () with S = 1/2 and [Zn(II)(L(2-))(L(0))] () with S = 1. This electron transfer is in agreement with the general trend in the redox potentials of the first row transition metal ions from Mn(ii) to Zn(ii), and it allows us to prepare and stabilize reversibly switchable tautomeric forms in transition metal complexes with redox-active ligands.
dc.language.isoen
dc.publisherRoyal Society of Chemistry
dc.title.enSwitching and redox isomerism in first-row transition metal complexes containing redox active Schiff base ligands.
dc.typeArticle de revue
dc.identifier.doi10.1039/C4DT01699H
dc.subject.halChimie/Matériaux
bordeaux.journalDalton Transactions
bordeaux.page15958-15967
bordeaux.volume43
bordeaux.issue42
bordeaux.peerReviewedoui
hal.identifierhal-01075876
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01075876v1
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