Abstract
A series of complexes of formula [(NC)5FeII—NC—FeII(CN)4L]n−, with L = H2O, pyridine, isonicotinamide and 4-cyanopyridine were prepared in aqueous solution by substitution of the corresponding [FeII(CN)5L]n− ions into [FeII(CN)5H2O]3−. The mixed valent (II, III) and fully oxidized (III, III) complexes were also obtained. The (II, II) complexes were moderately stable toward dissociation into the mononuclear species, but the mixed-valent ions were properly characterized by UV-vis-NIR spectroscopy and electrochemistry. Distinctive intervalence (IV) bands were assigned in the NIR region, with the energy being dependent on the binding properties of L; the IV band energy also correlated with the redox potential at the [NC—Fe(CN)4L] fragment. By application of the Hush model, a valence-trapped situation was found for the [(NC)5FeIII—NC—FeII(CN)4L]n− ions. The class II behavior shows, however, a value of H ab, the electronic coupling factor, of ca. 1600cm−1, indicating a moderate-to-strong communication between the metal centers.
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