Redox Active Two-Component Films of Palladium and Covalently Linked Zinc Porphyrin–Fullerene Dyad

Abstract

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.

Two-component polymer films of palladium and fullerene with covalently linked crown ether voids: effect of cation binding on the redox behavior

“…This shift of reduction potential indicates that the polymeric phase grown on the electrode surface inhibits the process of palladium(II) and fullerene reduction. Similar behavior was observed for electrodeposition of films of palladium and other derivatives of fullerenes [37][38][39]. The morphology of both films is shown in Fig.…”

“…Recently, we developed an electrochemical procedure for the formation of two-component fullerene films based on the electroreduction carried out in a solution containing fullerene [32][33][34][35][36] or fullerene derivatives [37][38][39][40] and various transition metal complexes. In these polymers, fullerene moieties are covalently bonded to transition metal atoms or their complexes to form a polymeric network.…”

“…These materials exhibit electrochemical activity in the negative potential range due to rich electroreduction of the fullerene moieties. Films containing fullerene derivatives with covalently attached redox probe, ferrocene, zinc porphyrin, or single-wall carbon nanotubes additionally show electrochemical activity at positive potentials [37][38][39]. In this case, the oxidation of electron-donating redox groups attached to the main backbone of the polymer is responsible for the anodic redox activity.…”

Electrochemically formed two-component films comprised of fullerene and transition-metal components

“…Related films are readily prepared by the reduction of C 60 and C 70 in the presence of limited amounts of dioxygen in a toluene/acetonitrile mixture [39,40]. A two-component electroreductive process that involves the reduction of C 60 (or a C 60 derivative) in the presence of transition-metal complexes of Pt, Pd, Ir, and Rh has been developed [41][42][43][44]. The fullerene/ transition-metal films that result are particularly interesting.…”

Comparison of electrochemical properties of two-component C60-Pd polymers formed under electrochemical conditions and by chemical synthesis

“…Recently, we developed an electrochemical procedure for the formation of two-component fullerene films based on the electroreduction carried out in a solution containing fullerene [45][46][47][48][49][50] or fullerene derivatives [51][52][53][54] and various transition metal complexes. In these polymers, fullerene moieties are covalently bonded to transition metal atoms or their complexes to form a polymeric network.…”