Abstract
The methyl viologen dication (MV2+) is electron deficient and readily undergoes outer-sphere charge-transfer complexation with donor species. Equilibrium constants of complexation (K) have been determined optically for a series of nine donors; some were found to form charge-transfer complexes while others merely formed association ion pairs. K is directly related to the ionization energy I of the donor moiety. For hexacyanoferrate(ii), the transition dipole of complexation is anomalously large. A plot of the spectral width at half peak height against standard functions from classical electrostatics is also given, and is discussed in terms of the CT transition incorporating molecular movement. The absorbance of an optical charge-transfer (CT) band decreases as an inert electrolyte is added to the solution. A simple treatment of a competing association reaction is used to explain why the absorbance (Abs) changes with anion concentration [X−], according to the relationship log(Abs)=klog([X−])+k′, where k and k′ are collections of constants.
Published Version
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