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Complexation of polyaniline with Lewis acids - a Mössbauer spectroscopy study

Bieńkowski K., Oddou J., Horner O., Kulszewicz-Bajer I., Genoud F., Suwalski J., Pron A.

Nukleonika

2003

Vol. 48,suppl.1

3-7

Doping with Lewis acid is a new method for improving solution processibility of conductive polyaniline. We report here detailed Mössbauer spectroscopy studies of polyaniline complexed with Lewis acids containing Mössbauer active nuclei, namely SnCl4 and FeCl3. Films of Lewis acid doped polyaniline cast from nitromethane solutions show stoichiometries of PANI(MeCln)1(CH3NO2)1 (where n = 3 or 4, Me denotes Sn or Fe and PANI denotes one aniline repeat unit), which means that both types of polyaniline nitrogens (imine and amine) participate in the complexation reaction, and one solvent molecule is introduced in the polymer matrix per one Lewis acid molecule. Mössbauer parameters of polyaniline doped with SnCl4 are consistent with hexacoordinated Sn(IV) in an environment of non-equivalent ligands. The spectrum of PANI doped with FeCl3 consists of two doublets with distinctly different Mössbauer parameters, which can be ascribed to two types of complexing sites (amine and imine nitrogens). From the temperature dependence of the isomer shift and the recoil free absorption, we have calculated the Mössbauer lattice temperature, ?m, as probed by both complexing sites, which are 83 K for amine and 126 K for imine sites.