Olaya, Astrid JohanaSchaming, Delphine HenrietteBrevet, Pierre-François MarieNagatani, HirohisaZimmermann, TomasVanicek, JiriXu, Hai-JunGros, Claude P.Barbe, Jean-MichelGirault, Hubert2012-02-072012-02-072012-02-07201210.1021/ja2087322https://infoscience.epfl.ch/handle/20.500.14299/77572WOS:000301084200085The self-assembly of the oppositely charged watersoluble porphyrins, cobalt tetramethylpyridinium porphyrin (CoTMPyP4+) and cobalt tetrasulphonatophenyl porphyrin (CoTPPS4−), 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 CoTMPyP4+/ CoTPPS4− complex and its capability to bind oxygen.Immiscible Electrolyte-SolutionsPolarizable Continuum ModelWater-Soluble Porphyrins2Nd-Harmonic GenerationLiquid/Liquid InterfaceCobalt Porphyrins2Nd DerivativesRadical CationEnergyDioxygentext::journal::journal article::research article