Ionic Self-Assembled Redox-Active Polyelectrolyte−Ferrocenyl Surfactant Complexes: Mesomorphous Structure and Electrochemical Behavior

Abstract

Redox-active polyelectrolyte−surfactant complexes (PSC) were prepared via the ionic self-assembly of sodium poly(styrenesulfonate) (PSS) and ferrocenyl surfactant, n-alkyl (ferrocenylmethyl)ammonium bromide (Fcn, n = 8, 12, 16, where n is the carbon number of the alkyl chain), in solution. The PSS−Fcn complex exhibited an ordered lamellar mesomorphous structure with the long period of d = 2.49, 2.94, and 3.74 nm for PSS−Fc8, PSS−Fc12, and PSS−Fc16, respectively. With increasing the length of surfactant alkyl chain, the stacking order was improved. Interestingly, in the solid complex, the ferrocenyl moieties formed H-aggregation showing an increase in the π−π* energy transfer of cyclopentadienes in the ferrocene moieties as known from the blue shift in the UV spectrum. These complexes showed higher thermal stability compared with their components due to the ionic interaction. Cyclic voltammogram (CV) measurements indicated that the electrode process of these redox-active complex films was diffusion-control...