Dimerization of metallated pigments as primary step in the construction ofmembrane gaps on gold, polymeric wires and isolable micelles

beta-Octasubstituted porphyrins form face-to-face dimers in solution, which are stabilized by pi-pi' interactions in case of pi-radical formation. Pol ymerization of viologen substituted zinc porphyrins leads depending on ster eochemistry to micelles or wire pairs. Anionic porphyrins were also adsorbe d to gold electrodes or colloids and entrapped in membrane gaps. Heterodime rization of these porphyrins adsorbed to solid phase surfaces and entrapped within a 2 nm membrane gap was detectable by fluorescence quenching. Ruthe nium complexes with two bipyridyl and one dioctadecyl dipyridyl methylene m alonate ligand form head-to-head dimers in aqueous solution. The octadecyl substituents of the dimer constituents point to opposite directions and lar ge multilayer micelles are formed upon aggregatetion in water. They survive drying. Dimerization processes are discussed as common basis for the forma tion of four uncommon supramolecular assemblies.