A series of tetrakis(arylethynyl)benzenes and bis(dehydrobenzoannuleno)benzenes have been synthesized containing tetra-substitutions of neutral, donor, and mixed donor/acceptor groups. To ascertain the importance of substitutional and structural differences of the phenylacetylenes, the optical absorption and emission properties of each series have been examined. Conjugation effectiveness, electron density, planarity, and geometry of charge-transfer pathways are found to have a pronounced effect on the overall optical and material properties. Pyridyl analogues have also been prepared and studied for their emissive response to protons and metal ions. To provide further insight into the energy levels and electronic transitions present, computational studies of each system have been performed. This talk will present our latest result in the area.