The current study employs both theoretical and experimental methods to characterize the electronic properties associated with peripheral substitution on asymmetric phenazine and bisphenazine systems. Substituent groups include F, Cl, Br, and NO(2) with substitutions made at different positions on the heteroaromatic rings in order to assess the effects of substituent type as well as substituent position on the electronic properties. A comprehensive investigation on halogen substituents was conducted to determine the efficacy of either Cl or Br, specifically these substituents' ability to lower LUMO energies relative to F. HOMO and LUMO energy levels have been theoretically characterized using Density Functional Theory (B3LYP) with both 6-31G* and 6-31+G* basis sets. Theoretical results are compared to results obtained using UV-Vis spectroscopy and cyclic voltammetry. Additionally, a theoretical comparison of the smaller, phenazine molecule and the larger bisphenazine system has been conducted to ascertain whether the smaller system can be used to model the electronic properties of the larger molecule.