DFT studies of the structural, electronic, and electrochemical properties of copolymers containing ferrocene and imidazole

Ferrocene-based polymers have been used in various applications such as sensors, solar cells, batteries, and photo-oxidation of thin films. Copolymers containing ferrocene and imidazole are unique because of electronic interactions between the ferrocene and neighboring imidazole moiety, leading to the formation of charge transfer complexes in the polymer. Recent electrochemical and UV-Vis studies in the presence of various electrolytes containing metal ions have revealed significant modifications in their properties, e.g., red shifts, and the appearance of multiple oxidation waves in cyclic voltammetry studies. Even though these modifications have been attributed to the ability of the imidazole to coordinate with metal ions, increasing its electron deficiency, thereby enhancing oxidization of the nearby ferrocene moiety if it is in close proximity to it, the equilibrium geometry of the polymer complex is unknown. This talk will discuss the results of DFT studies that was used to address these concerns, for instance determination of equilibrium geometry, and frontier energy levels. We will also discuss the correlation of molecular orbital density plots to the electrochemical properties, specifically the formation of donor-acceptor complexes within the polymer.