Electrochemical polymerization of aniline investigated using on-line electrochemistry/electrospray mass spectrometry

A thin-layer electrochemical flow cell coupled on-line with electrospray mass spectrometry (EC/ES-MS) was used to investigate the soluble products from the controlled-potential anodic polymerization of aniline in H(2)O and H(2)O/CH(3)OH (1/1 v/v) with ammonium acetate and acetic acid or ammonium hydroxide as electrolytes (pH 4, 6.5, or 9). At a working electrode (glassy carbon) potential of 1.0 V versus Ag/AgCl, singly protonated aniline oligomers containing as many as 10 aniline units (10-mer) were observed in the ES mass spectra when the polymerization in H(2)O/CH(3)OH at pH 4 was carried out. The abundance of the higher n-mers decreased at higher solution pH and in 100% H(2)O at pH 4. Most of the oligomers were observed in more than one redox state ranging from fully oxidized (all imine nitrogens) to fully reduced (all amine nitrogens). The number of different redox states observed for the n-mers increased with increasing n. The structures of the reduced (m/z 185) and oxidized (m/z 183) aniline dimer ions (head-to-tail, tail-to-tail, or head-to-head) produced from the polymerization of aniline at pH 4, 6.5, and 9 in H(2)O/CH(3)OH were revealed to vary as a function of pH by comparison of their tandem mass spectrometry product ion spectra with the product ion spectra of the dimer standards. EC/ES-MS potential scan experiments, in which the working electrode current and major n-mer ions for n = 2, 3, and 4 were monitored as a function of electrode potential, were used to probe the growth mechanism to higher aniline oligomers. Under the conditions used, the controlled-current electrolytic process inherent to the operation of the ES ion source did not significantly influence the formation or nature of the oligomers observed. Beyond the current application, the results presented here serve to demonstrate the utility of EC/ES-MS as a tool in identifying the initial products of electropolymerization and in studying the products of electrode reactions in general.