Poly(N-methylaniline) vs. polyaniline: An extended pH range of polaron stability as revealed by Raman spectroelectrochemistry

[Display omitted] •Red laser line excitation of Raman spectra reveals polarons in polyaniline and poly(N-methyl)aniline.•Polarons in polyaniline are stable only in acidic, but not in pH-neutral environment.•Polarons in poly(N-methyl)aniline are stable both in acidic and neutral envirinment. A comparative study of polyaniline (PANI) and poly(N-methylaniline) (PNMA) has been performed by means of Raman spectroelectrochemical technique at 633 nm and 785 nm laser line excitations. The excitation wavelengths used fall into a resonance with the blue colored semi- and full-oxidized forms of these conducting polymers. The dependence of Raman features on electrode potential and solution acidity was studied, and relative content of polaronic and bipolaronic states was evaluated. In an acidic solution, the semioxidized emeraldine form of either PANI or PNMA exists in equilibrium between their polaronic and bipolaronic states. In a neutral or even slightly alkaline solution, this equilibrium for PANI shifts to bipolaron state, resulting in loss of its conductance. For PNMA, however, the relative content of polaron state appears high enough even in pH-neutral soulions, thus determining a higher conductivity of PNMA in pH-neutral environment as compared to that of PANI. A mechanistic interpretation for this, based on differences in the chemical structures of these polymers, is also presented.