Backbone structure ferrocene polymers

As shown in Scheme 11.Id, these polymers consist of the main backbone of (i) a nonconductive polymer (25-27), or a polymeric ionomer (29) or (ii) a backbone of an ECP (28) to which pendant, localized redox-centers, such as ferrocene (Fc), bipyridine-complexes of Ru, Os, and so forth, or even low-molecular-weight thiophene oligomers, are covalently attached (25, 27, and 26, respectively). Covalent attachment is characteristic of the structure 28, whereas 29 contains a typical electrostatic bond between the electroactive bipyridine-complex of Ru and the polymeric ionomer s backbone. 

Polymer networks are complex structures with anomalous dynamic properties. Measurements on polymers based on vinyl ferrocene showed a change in the temperature dependence of the recoil-free fraction between 80 and 180 K, which was independent of changes in the polymer backbone (Litterst, Lerf, Nuyken Alcala, 1982). In the same temperature region changes in the linewidths of the absorption lines were also observed. Both phenomena were explained by the thermally activated population of additional conformational substates. A copolymer swollen with dimethylformamide revealed a further sharp decrease in / near to 190 K. This decrease was interpreted in terms of a glass transition, where cooperative motions of large parts of the backbone become important. 

---