Self-assembled molecular rafts at liquid|liquid interfaces for four-electron oxygen reduction

  • Olaya A
  • Schaming D
  • Brevet P
 et al. 
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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.

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  • Astrid J. Olaya

  • Delphine Schaming

  • Pierre Francois Brevet

  • Hirohisa Nagatani

  • Tomas Zimmermann

  • Jiri Vanicek

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