title: Self-assembled molecular rafts at liquid|liquid interfaces for four-electron oxygen reduction.
abstract: The self-assembly of the oppositely charged water-soluble porphyrins, cobalt tetramethylpyridinium porphyrin (CoTMPyP(4+)) and cobalt tetrasulphonatophenyl porphyrin (CoTPPS(4-)), at the interface with an organic solvent to form molecular "rafts", provides an excellent catalyst to perform the interfacial four-electron reduction of oxygen by lipophilic electron donors such as tetrathiafulvalene (TTF). The catalytic activity and selectivity of the self-assembled catalyst toward the four-electron pathway was found to be as good as that of the Pacman type cofacial cobalt porphyrins. The assembly has been characterized by UV-visible spectroscopy, Surface Second Harmonic Generation, and Scanning Electron Microscopy. Density functional theory calculations confirm the possibility of formation of the catalytic CoTMPyP(4+)/ CoTPPS(4-) complex and its capability to bind oxygen.
authors: Laboratoire d'Electrochimie Physique et Analytique, Station 6, Ecole Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland.
authors: Astrid J
authors: AJ
authors: Olaya
authors: Delphine
authors: D
authors: Schaming
authors: Pierre-Francois
authors: PF
authors: Brevet
authors: Hirohisa
authors: H
authors: Nagatani
authors: Tomas
authors: T
authors: Zimmermann
authors: Jiri
authors: J
authors: Vanicek
authors: Hai-Jun
authors: HJ
authors: Xu
authors: Claude P
authors: CP
authors: Gros
authors: Jean-Michel
authors: JM
authors: Barbe
authors: Hubert H
authors: HH
authors: Girault