Poly(ferrocenylsilanes): novel organometallic plastics

Poly(ferrocenylsilanes) are a novel class of transition metal-containing macromolecules with a backbone that consists of alternating ferrocene and organosilane units. High molecular weight examples of these interesting materials were first prepared several years ago by thermal ring-opening polymerization (ROP) of silicon-bridged [1]ferrocenophanes ([1]silaferrocenophanes). This Feature Article discusses current knowledge of the properties of these readily available and processable organometallic polymers together with recent developments made possible by the discovery of living anionic and transition metal-catalyzed ROP routes. These methodologies have provided ambient temperature access to poly(ferrocenylsilanes) with molecular weight control and also to well defined architectures such as block copolymers. The latter materials self-assemble in the solid state to form ordered arrays of nanoscale redox-active organometallic domains and in solution form well defined supramolecular organometallic polymer aggregates such as spheres, cylinders, and more complex architectures.