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.

Bis(imino)acenaphthene zinc complexes with methylated aryl substituents have been examined from the standpoint of their photoluminescent properties. Although complexes 1–4 proved to be nonemissive in solution, complexes 1 and 2 were found to emit via an aggregation-induced emission pathway. On the other hand, complexes 3 and 4 were found to be nonemissive in the solid state. Detailed crystallographic studies of complexes 1–4 provided valuable insights into the structural differences between the emissive (1 and 2) and nonemissive complexes (3 and 4), particularly with respect to their molecular structures and crystal-packing environments. TD-DFT theoretical calculations were carried out and were found to support the hypothesis that the phosphorescent emissions of 1 and 2 are due to the existence of intermolecular π-stacking interactions within the crystal lattices. Finally, a series of solvatomorphs of complexes 1 and 2 were synthesized and their emissive properties were studied.

The synthesis, characterization, and theoretical study of the sterically directed functionalization of the redox-active bis(imino)acenaphthene (BIAN) ligand class has been explored. With dependence on the steric congestion encompassing the N–C–C–N fragment of the Ar-BIAN ligand, functionalization can be directed to proceed either via a radical backbone dearomatization or a nucleophilic imine C-alkylation pathway. The structures of the Ar-BIAN derivatives 14–19 were determined by means of single-crystal X-ray diffraction. The reaction pathways involved in Ar-BIAN functionalization were monitored by means of EPR spectroscopy. The experimental results and observations were examined in conjunction with DFT-D calculations in order to explain the driving forces that direct the pathways leading to Ar-BIAN functionalization.

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.