An Access Route to Polyferrocenes via Modular Conjugation

The application of copper‐catalyzed azide/alkyne cycloaddition to monomers containing a ferrocene unit leads to polyferrocenes with ferrocene in the backbone. Catalyst performance and kinetic studies of a model system comprising 1,1'‐bis(azidoethyl)ferrocene and propargyl ether revealed the usage of CuI and DBU as the catalyst in DMF at 50 °C as efficient reaction conditions for the synthesis. The resulting polymers display molecular weight‐averages up to $\overline {M} _{{\rm n}} $  = 10 000 and $\overline {M} _{{\rm w}} $  = 33 000. The polyaddition of monomers both containing ferrocene units led to polyferrocenes with $\overline {M} _{{\rm n}} $ between 4 000 and 11 000 ( $\overline {M} _{{\rm w}} $ up to 78 000). The present study thus provides a pathway to polyferrocenes based on modular ligation chemistry.