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Binuclear manganese(III) complexes with carboxylate bridges: Synthesis, structure, electrochemistry and magnetic properties

Authors
Journal
Polyhedron
0277-5387
Publisher
Elsevier
Publication Date
Volume
25
Issue
7
Identifiers
DOI: 10.1016/j.poly.2005.11.022
Keywords
  • Binuclear Complexes
  • Manganese(Iii)
  • Carboxylate Bridges
  • Crystal Structure
  • Electrochemistry
  • Magnetochemistry
Disciplines
  • Physics

Abstract

Abstract A series of μ-oxo, μ-carboxylato binuclear manganese(III) complexes derived from bipy, phen and different carboxylate ligands have been prepared and characterized by IR and UV–vis spectroscopies, cyclic voltammetry, magnetic susceptibility and the X-ray crystallography. The electronic spectra of all the complexes show very similar features consisting of two absorptions in the visible region, one high intensity LMCT band and two intra-ligand transitions in the UV region. The cyclic voltammograms of the complexes exhibit four steps in most cases, each consisting of a one-electron transfer reaction. These probably correspond to Mn 2 III ↔ Mn IV Mn III ↔ Mn 2 IV oxidation and Mn 2 III ↔ Mn III Mn II ↔ Mn 2 II reduction processes. The structure of complex 2 has been determined by the X-ray crystallography and consists of a binuclear [Mn 2(bipy) 2(μ- O)(μ-OOCR) 2(NO 3)(H 2O)] + cation (R = CH 2Cl) with a ClO 4 - anion. Low temperature magnetic susceptibility measurements show that there is a weak ferromagnetic interaction in 1 (R = Ph) ( J = +0.43 cm −1) and a weak antiferromagnetic interaction between the metal centers in 2 (R = CH 2Cl) ( J = −0.15 cm −1).

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