Soluble polymethacrylates and polystyrenes containing cationic cyclopentadienyliron moieties

Cyclopentadienyliron coordinated chloroarenes were utilized to synthesize novel classes of cationic organoiron methacrylate and styrene monomers via metal-mediated nucleophilic aromatic substitution reactions. These monomers were subsequently polymerized using a radical initiator to produce the corresponding organoiron polymers. Polymerization of olefin-containing monomers containing terminal chloroarene complexes was also achieved by reaction with dinucleophiles yielding organoiron-coordinated polyaromatic ethers and ether-thioethers with pendent methacrylate or styrene moieties. These soluble polymers were subsequently crosslinked with a radical initiator, which resulted in the isolation of insoluble networks. Cyclic voltammetric investigations of these polymers showed that the inpendent cationic iron centers underwent reversible reduction. Thermogravimetric analysis showed that the cyclopentadienyliron complexes were cleaved from the polymer backbones at approximately 220degreesC, however; depending on the architecture of the polymer backbones, their structural integrities held from 320 to 470degreesC. The solubilities of the polymethacrylates were much higher in comparison to polystyrene T analogues and had weight average molecular weights between 22 500 and 86 400 with polydispersities ranging from 1.4 to 2.6. The molecular weights of the cationic organoiron polymers prepared via nucleophilic aromatic substitution polymerization ranged from 10500 to 22800 with polydispersities of 1.2 to 1.7.