Cyclic Siloxanes and Silsesquioxanes as Cores and Frameworks for the Construction of

siloxane as core, novel ferrocenyl silicon-con-taining dendrimers have been constructed up to the third generation, which contains 16 periph-eral ferrocene moieties. As precursors of these ferrocenyl dendritic molecules, Si—Cl- and Si— allyl-terminated cyclotetrasiloxane-based den-drimers were also built step by step, by the repetition of hydrosilylation and alkenylation reactions as growing steps. The dendritic struc-tures have been confirmed by 1H, 13C and 29Si NMR, infrared spectroscopy, elemental analysis, mass spectrometry and vapor-pressure osmo-metry. Solution electrochemical studies showed that all the ferrocenyl redox centers attached to the dendritic surface behave as independent, electronically isolated units, so that the dendri-mers exchange all the electrons simultaneously at the same potential. We also describe the application of the first redox-active ferrocenyl polymer containing an octakis(dimethyl-siloxy)octasilsesquioxane framework, as a med-iator in the electrocatalytic oxidation of ascorbi