Micro and nano-sized polysiloxanes containing organoiron moieties

Utilizing organoiron-mediated nucleophilic aromatic substitution, a number of allylamine-containing organoiron complexes were prepared. Amide formation between 1,1'-ferrocene dicarbonyl chloride and allylamine produced a similar ferrocene compound. These materials were subjected to hydrosilation with methyldiethoxyhydrosilane to generate cationic organoiron siloxanes and ferrocene-containing siloxane complexes. Electrochemical analysis of the allylamine and siloxane complexes showed redox couples characteristic of nitrogen-substituted arene-coordinated cyclopentadienyliron complexes. In situ cleavage of the ethoxy groups followed by the addition of H2SO4 resulted in the formation of polymeric materials. Thermal analysis revealed that the cationic organoiron moieties decomposed between 200 degrees C and 250 degrees C, whereas the ferrocene moiety decomposed at 110 degrees C and the backbones of the polymers began to decompose above 400 degrees C. The polymers displayed glass transition temperatures between 68 degrees C and 111 degrees C. Scanning electron microscopy showed that the polymers possessed very different morphologies, ranging from particulates to crystalline.