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

• Published in: Macromolecular symposia. 2000-07, Vol.156 (1), p.11-20
• Main Authors: Fuhrhop, J�rgen-Hinrich, Böttcher, Christoph, Draeger, Christian, Fudickar, Werner, Schulz, Andrea, Messerschmidt, Christian, Zimmermann, J�rg
• Format: Article
• Language: English
• Subjects: Dimerization; Dimers; Gold; Membranes; Micelles; Porphyrins; Wire; Zinc
• ISSN: 1022-1360; 1521-3900
• DOI: 10.1002/1521-3900(200007)156:1<11::AID-MASY11>3.0.CO;2-H

β‐Octasubstituted porphyrins form face‐to‐face dimers in solution, which are stabilized by π‐π′ interactions in case of π‐radical formation. Polymerization of viologen substituted zinc porphyrins leads depending on stereochemistry to micelles or wire pairs. Anionic porphyrins were also adsorbed to gold electrodes or colloids and entrapped in membrane gaps. Heterodimerization of these porphyrins adsorbed to solid phase surfaces and entrapped within a 2 nm membrane gap was detectable by fluorescence quenching. Ruthenium complexes with two bipyridyl and one dioctadecyl dipyridyl methylene malonate ligand form head‐to‐head dimers in aqueous solution. The octadecyl substituents of the dimer constituents point to opposite directions and large multilayer micelles are formed upon aggregatetion in water. They survive drying. Dimerization processes are discussed as common basis for the formation of four uncommon supramolecular assemblies.