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Tuneable electronic coupling in linked bis(cubane) cobalt-oxo clusters
Vincent J P Maddi1,2, T Don Tilley1,2
1Department of Chemistry, University of California Berkeley California 94720 USA tdtilley@berkeley.edu.
None:
A family of cobalt-oxo bis(cubane) complexes wherein each subunit is derived from the Co4O4 cubane, a known water oxidation catalyst, was synthesized. Both 4,4'-bipyrdine and pyrazine were demonstrated to serve as viable bridging ligands. Through an analysis of their half-wave splitting potentials, it was determined that pyrazine-bridged bis(cubane)s exhibit inter-cubane electronic coupling, and that this coupling may be tuned through ligand substitution. Electrostatic contributions to the half-wave splitting potentials were evaluated and found to result in "non-conformist" behavior related to the ion-pairing ability of the electrolytes.
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