Photooxidation and photoconductivity of polyferrocenylsilane thin films

Irradiation of thin films of poly(ferrocenyl-methylphenylsilane) ([Fe(η⁵-C₅H₄)₂ SiMePh]_n) cast from chloroform solution with UV light leads to photooxidation of ferrocene centers in the polymer main chain. The extent of the polymer oxidation can be controlled in the range ca. 0-5% by the duration of the irradiation exposure and by the concentration of chloroform. The photooxidized polyferrocenylsilane material is conductive, with an increased conductivity of greater than three orders of magnitude relative to the unoxidized material. In addition, the photooxidized polymers have been found to be photoconductive. The photooxidation process can be reversed by means of chemical reduction using hydrazine or decamethylferrocene, leading to the regeneration of the neutral polymers. However, substantial molecular weight decline was detected during the photooxidation/reduction process, presumably as a result of chain cleavage reactions induced by the anionic or radical chlorinated photoproducts. Methylation of the cyclopentadienyl rings of the ferrocene moiety in the polymer was found to lead to materials which are significantly more stable.