Photoelectrochemistry and spectroscopy of substituted polyanilines

The properties of four substituted polyanilines, poly(N-methylaniline), poly(m-methylaniline), poly(o-methoxyaniline), and poly(o-ethoxyaniline) have been examined by photoelectrochemical and spectroscopic techniques (Raman and XPS). The middle peak in cyclic voltammograms for poly(N-methylaniline) was ascribed to hydrolysis products such as benzoquinone, and in the case of poly(o-methoxyaniline) to branched forms. The photocurrent profiles of the substituted polyanilines resembled those of polyaniline to a large extent, with prolonged cathodic and anodic photocurrents given for the polymer in a state of high conductivity. With poly(o-ethoxyaniline) only short-lived photocurrents were obtained pointing to a more highly insulating material, also shown by the limited growth of this polymer. Raman spectra of the substituted polyanilines taken in situ revealed typical polyaniline Raman bands, while the largest shift in the υ_CN band (35 cm⁻¹) occurred with poly(N-methylaniline). A deconvolution of the N 1s signal in XPS scans showed nitrogens consistent with oxidised forms of the polymers: a high proportion of positively charged nitrogens for poly(N-methylaniline) and of imine nitrogens for poly(m-methylaniline).