Here we report the characterization of diquinolines derivatives with ambipolar character. The investigated derivatives show low p- and moderately low n-doping redox systems. The derivatives were investigated and the electro-chemical and optical properties of these compounds measured, with attempts to correlate the properties with their π-electron conjugation lengths. We showed the marked influence of the heteroatom in the bridge (central ring) and geometry of the molecule with its electronic properties. The compounds were compared by UV-Vis-NIR and EPR spectroelectrochemistry indicating very different charge and spin properties dependent on the heteroatoms present. Finally the OLED devices were formed and characterized.