Spectroelectrochemical Studies of Charge Transfer Processes in Stable Nitroxyl Radical-Containing Polymers
We have employed potential modulated spectroelectrochemical techniques for our study of stable radical polymer systems whereby, kinetic information can be determined, specifically rates of charge transfer and ion diffusion within our polymer systems. A key factor determining the success of such experiments is that the material of interest exhibits a strong absorption coefficient and allows for measurement in the concentration regime conducive for electrochemical studies (typically up to 10 mM). For this reason, of the available stable nitroxyl radical systems, we have chosen first to study the oxidation of a nitronyl nitroxide derivative. To simulate an electrode architecture, spectroelectrochemical studies were performed in the solid state, and the efficacy of charge transfer was investigated as a function of film thickness, counter-ion size, and radical polymer composition. As we have developed a synthetic process to produce ordered systems of stable organic radicals in the form of fixed polymer brushes grown from transparent conducting substrates, the effects of nano- and mesoscale ordering of the polymer film on charge transfer dynamics will also be presented.