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

Sasmal, Ashok and Garribba, Eugenio and Gómez-García, Carlos J. and Desplanches, Cédric and Mitra, Samiran (2014) Switching and redox isomerism in first-row transition metal complexes containing redox active Schiff base ligands. Dalton Transactions, Vol. 43 (42), p. 15958-15967. ISSN 1477-9226. eISSN 1477-9234. Article.

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DOI: 10.1039/C4DT01699H

Abstract

The reversible redox isomerisms in first row transition metal complexes of the type ML2 were studied. The six ML2 complexes (M = MnIII (1), FeII (2), CoIII (3), NiII (4), CuII (5) and ZnII (6)) 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 (L2−, L and L0). EPR spectra and magnetic susceptibility measurements indicate the presence of complexes of the type [MnIII(L2−)(L)] (1) with S = 1/2, [FeII(L−)2] (2) with S = 2, [CoIII(L2−)(L)] (3) with S = 1/2, [NiII(L)2] (4) with S = 1, [CuII(L−)2] (5) with S = 1/2 and [ZnII(L)2] (6) 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 (1, 2, 4) or ligand-to-ligand (in 5, 6) electron transfer (partial or total), resulting in compounds of the type [MnIV(L2-)2] (1′) with S = 1/2, [FeIII(L−)(L2−)] (2′) with S = 1, [NiIII(L2−)(L−)] (4′) with S = 0, [CuII(L2−)(L0)] (5′) with S = 1/2 and [ZnII(L2−)(L0)] (6′) 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.

Item Type:Article
ID Code:10736
Status:Published
Refereed:Yes
Uncontrolled Keywords:Reversible redox isomerisms, Schiff base ligand, first-row transition metal complexes, redox active Schiff base ligands
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 01-a Nuovi Dipartimenti dal 2012 > Chimica e Farmacia
Publisher:Royal Society of Chemistry
ISSN:1477-9226
eISSN:1477-9234
Deposited On:02 Feb 2015 13:51

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