The stable redox properties of ferrocene/ferrocenium have been used to investigate ferrocene-based functional materials. Herein, the steric effects of an exterior cage on the redox properties of interior metallocenes have been investigated using cyclic voltammetry measurements of ferrocene-diyl bridged macrocages and their noncage isomers. As the half-wave potential (E1/2) depends on ferrocenium stabilization through solvation, positive shifts in the E1/2 were observed in the macrocages. As peak separation between potentials of the anodic and cathodic peaks depends on the rate of electron transfer, marked broadening from the ideal value was observed in the macrocages due to the insulating effect of the outer cage. These steric effects of the cage on the redox properties of ferrocenes could aid the molecular design of metallocene-based functional molecules.
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