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Highly stable, supramolecular assembled layers with 1:1 composition of C60 and C70 fullerenes were found to form on nickel(II) octaethylporphyrin (NiOEP)-modified Au(111) surface, whereas the replacement reaction of the first adlayer of nickel(II) tetraphenyl porphyrin (NiTPP) occurred upon adsorption of fullerene molecules as the second layer. This result shows that supramolecular assemblies of C60 and C70 are strongly influenced by the underlying layer of porphyrin. It is demonstrated that the stability of the first adlayer is an important factor in the surface design of host-guest selectivity of fullerenes on electrode surfaces.

Effect of Underlying Ni(II) Porphyrin Adlayer on the Formation of Supramolecular Assembly of Fullerenes on Au(111) in Solution