Redox-active systems supramolecular development

Up until 1977, the non-covalent polymeric assemblies found in biological membranes rarely attracted any interest in supramolecular organic chemistry. Pure phospholipids and glycolipids were only synthesized for biophysical chemists who required pure preparations of uniform vesicles, in order to investigate phase transitions, membrane stability and leakiness, and some other physical properties. Only very few attempts were made to deviate from natural membrane lipids and to develop defined artificial membrane systems. In 1977, T. Kunitake published a paper on A Totally Synthetic Bilayer Membrane in which didodecyl dimethylammonium bromide was shown to form stable vesicles. This opened the way to simple and modifiable membrane structures. Since then, organic chemists have prepared numerous monolayer and bilayer membrane structures with hitherto unknown properties and coupled them with redox-active dyes, porous domains and chiral surfaces. Recently, fluid bilayers found in spherical vesicles have also been complemented by crystalline mono-... 

Also other active metal complexes (i.e., several Co SchifF base [232] and Mn diimine complexes [233]) have been supported in this way. The high dispersion of the complexes in the cages of the molecular sieves allows to study the redox properties of mononuclear complexes that are imstable in solution [234]. The increased stability of the obtained materials, the easier handling of heterogeneous catalysts and the high yields achieved make these supramolecular systems a very promising candidate for further catalyst development in fine chemical synthesis. 

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