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Dinuclear Complexes Formed by Hydrogen Bonds: Synthesis, Structure and Magnetic and Electrochemical Properties
Matteo Granelli1, Alan M Downward1, Robin Huber1
1Department of Inorganic and Analytical Chemistry, University of Geneva, 30 quai Ernest Ansermet, 1211, Geneva 4, Switzerland.
Abstract:
The synthesis is reported of a series of homo- and hetero-dinuclear octahedral complexes of the ligand 1, 1,2-bis(1-methyl-benzimidazol-2-yl) ethanol, where the two metal centres are linked by hydrogen bonds between coordinated alcohols and coordinated alkoxides. Homonuclear divalent MII MII , mixed-valent MII MIII and heteronuclear MII M'III species are prepared. The complexes have been characterised by X-ray crystallography and show unusually short O⋅⋅⋅O distances for the hydrogen bonds. Magnetic measurements show the hydrogen-bond bridges can lead to ferromagnetic or antiferromagnetic coupling. The electrochemistry of the dinuclear species is significantly different from the mononuclear systems: the latter show irreversible waves in cyclic voltammograms as a result of the need to couple proton and electron transfer. The dinuclear species, in contrast, show reversible waves, which are attributed to rapid intramolecular proton transfer facilitated by the hydrogen-bonded structure.
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