Protonation of leucoemeraldine in the solid state and in solution

The protonation of leucoemeraldine in power form and in N‐methylpyrrolidinone (NMP) solution by HCIO4 and HBF4 has been studied by x‐ray photoelectron spectroscopy (XPS), infrared (IR), and ultraviolet (UV)‐visible absorption spectroscopy. In powder form, less than 25% of the amine nitrogens can be protonated in the absence of oxygen. The effects of oxygen on the degree of protonation and the distribution of amine and imine units upon deprotonation of the salt are investigated. The degree of protonation in leuccemeraldine can be increased to about 50% with 3 M HCIO4, similar to that achievable with emeraldine base in powder form. In NMP solution, leucoemeraldine is easily oxidized by dissolved oxygen. Protonation of both leucoemeraldine and emeraldine base in NMP solutions results in metastable species which gradually undergo deprotonation. The resulting products are affected by the O2 content of the solutions.