This article demonstrates that new redox active films can be electrochemically generated by reduction of a chemically modified fullerene (the ferrocene-fullerene conjugate 2′ferrocenylpyrrolidino-[3′,4′;1,2][C 60 ]fullerene, Fc-C 60 ) and [Pd(ac) 2 ] 3 . These films are electrochemically active in both positive and negative potential regions. The formation and electrochemical properties of this Fc-C 60 /Pd film have been studied using cyclic voltammetry and electrochemical quartz crystal microbalance techniques. The surface morphology and infrared spectra of the film are also reported. At negative potentials, the electrochemical behavior of the new Fc-C 60 /Pd film shows features similar to the ones displayed for the previously studied C 60 /Pd film. In the positive potential range, peaks related to chargetransfer processes of the ferrocene units linked to the polymer backbone are observed. Reduction of the film at negative potentials is accompanied by transfer of cations at the solution/film interface and their transport inside the solid phase. On the other hand, the transport of the anions is involved in the process of film oxidation. The film exhibits higher permeability to the anions than to the cations. The oxidation process results in significant changes of the structure and morphology of the ferrocenylfullero[C 60 ]pyrrolidine/Pd film. Electrostatic interaction between positively charged ferrocene groups and negatively charged fullerene units within the film significantly modify the redox properties of ferrocene units. The electrochemical properties and the film structure depend also on the concentrations of the precursors in the growth solution.

Redox active films have been generated electrochemically by the reduction of dyads consisting of fullerene C 60 covalently linked to zinc meso-tetraphenyloporphyrin, ZnPÀC 60 , and palladium acetate. The films are believed to consist of a polymeric network formed via covalent bonds between the palladium atoms and the fullerene moieties. In these films, the zinc porphyrin moiety is covalently linked to the polymeric chains through the pyrrolidine ring of the fullerene. The ZnPÀC 60 /Pt films are electrochemically active in both positive and negative potential excursions. At positive potentials, two oxidation steps for the zinc porphyrin are observed. In the negative potential range, electron transfer processes involving the zinc porphyrin and the fullerene entities are observed. Film formation is also accompanied by palladium deposition on the electrode surface. The presence of a metallic phase in the film influences its morphology, structure and electrochemical properties.

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