We have prepared a series of monomers with the general formula diphenylamine-R-diphenylamine. The electro-oxidation of these monomers in a series of non-aqueous solvents leads to para C-C coupling of the terminal phenyl rings to produce (R-diphenyl benzidine)(n), an alternating main chain unit material. Polymeric material is formed from high-polarity solvents while low-polarity solvents produce precipitated oligomeric materials. Low-energy ( similar to 0.8 eV) charge-transfer bands can be observed in the 1 e(-) per repeat unit oxidized thin film precipitated oligomeric material. The thin film polymeric material does not show these charge-transfer bands. These bands show polarization parallel with respect to the surface. Since these materials lack conjugation along the chain, pi-stacking between chains with a stacking axis parallel to the surface is most likely responsible for these electronic transitions. Thus this system self-organizes upon formation at the surface.