Marcus theory states that the rate of charge transfer is directly proportional to the amount of intermolecular orbital overlap. Theoretically optimizing the electronic coupling through the orientation and distance which both can increase the frontier orbital overlap between molecules is an attractive route to potentially provide theoretical insight for discovering new high performance semiconductor materials. To investigate how these parameters qualitatively affect charge transfer of model systems, unconstrained dimer optimizations with MP2 and dispersion-corrected DFT methods were used to probe the pi-pi interactions of methylated, fluorinated, and trifluoromethylated benzene, pyridine, and bipyridine dimers. These systems can serve as simplified models representing weak noncovalent interactions in organic semiconductor materials. Enhanced intermolecular interaction energies, reduced pi-pi distances, and more favorable cofacial orientations were found with the trifluoromethylated dimers compared to fluorinated and methylated dimers studied. Similar effects were found with donor-acceptor pairs that represent organic p-n heterojunction systems. These enhanced pi-pi interactions are likely caused by increased molecular quadrupole moment and dispersion interaction associated with trifluoromethylation. This computational study illustrates the strong potential of trifluoromethylation and, possibly perfluoroalkylation of acenes and heteroacenes, leading qualitatively to enhanced electron transfer through better pi-pi stacked structures, making them viable candidates for use as n-type organic semiconductor materials. The findings also provide insight for fundamental interactions between drug molecules that include fluorinated and trimethylfluorinated aromatics binding to protein receptors.