Bis(imino)acenaphthene (BIAN) zinc complexes with para-substituted aryl groups have been synthesized and investigated from the standpoint of their photophysical properties. Each complex was found to be nonemissive in solution. However, complexes 1–6 turned out to be emissive in the solid state, while complexes 7 and 8 remained nonemissive. The emissions for complexes 1–8 displayed color tunability ranging from red-yellow. A detailed crystallographic study of the “as-synthesized” structures revealed a distinct difference in the crystal packing environments of the emissive and nonemissive complexes. Furthermore, a solvatomorphic study provided further emission tunability via changes in the crystal packing environments of each solvatomorph. Lastly, TD-DFT calculations were performed in order to investigate the effect of different para-substituents on the flanking aryl rings of the BIAN ligand.