Smart organometallic polymer platforms for redox sensing and as metal nanoparticle foundry

In this Thesis, we aimed at developing novel tailored architectures and exploring rationally designed systems as redox active platforms for specific functions with organometallic polymer poly(ferrocenylsilane)s (PFSs). The preparation and characterization of various PFSs are described, including virtually unexplored structures. PFSs are a fascinating class of processable materials with redox characteristics suitable for the modification of surfaces and electrodes and have significant potential in the electrochemical detection of biological analytes. First we embarked on the quest to enhance the range of applications of surface bound PFS for sensing. To this end, we developed new strategies to immobilize the polymer on electrodes by electrografting, layer-by-layer deposition in combination with covalent coupling and simple grafting to methods. These redox-active interfaces displayed excellent sensing abilities towards ascorbic acid and hydrogen peroxide. As we primarily aimed at biomedical applications, we mainly focused on water soluble PFS systems, including polyionic liquids and hydrogels. Inherent to the redox responsive behavior, PFS hydrogels have the ability to reduce metal ions that exhibit oxidation potentials exceeding the value typical for ferrocene. We tackled the question of making various PFS hydrogel structures, which could be swollen by electrolytes including the metal ions of interest. In the reduction process without the use of any external reducing agents, metal nanoparticles form upon exposing the salt solutions to the PFS hydrogel. These particles can be further used in sensing, in catalysis and for antimicrobial surfaces. This PFS hydrogel platform that we call “metal nanoparticle foundry” was established in bulk gels and gel films, and some applications were illustrated.