This thesis is based on a research project aimed at the selective modification of the known cyclopenta-fused polycyclic aromatic hydrocarbon (CP-PAH) based electron acceptor cyclopenta[hi]aceanthrylene. Starting form 2,7-bis(trimethylsilyl)cyclopenta-[hi]aceanthrylene, we utilized bromination and/or C-H activation strategies that could orthogonally functionalize the cyclopenta[hi]aceanthrylene core. Depending on which reagents were utilized, aromatic substitutions could be directed to either the five-membered rings or the six-membered rings. The functionalization location had dramatic effects on the resulting material's optical band gap with the highest occupied molecular orbital being most affected. We further demonstrate how these materials are good electron acceptors through cyclic voltammetry as well as a fluorescence quenching experiments with poly(3-hexylthiophene). Lastly, we have extended the described functionalization strategy to dicyclopenta[de,mn]tetracene based CP-PAHs.