A comprehensive analysis of electronic transitions in naphthalene and perylene diimide derivatives through computational methods

Abstract Perylene diimide (PDI) and naphthalene diimides (NDIs) are compounds widely used in supramolecular structures due to their versatile and functional properties. They have high absorptions and photoluminescence capabilities, which make them ideal for electronic transition studies. Reflux method, a widely employed synthetic technique, was utilized to synthesize NDI and PDI derivatives. In this method, the respective amino acids and NTDA (naphthalene‐1,4,5,8‐tetracarboxylic dianhydride) were combined in acetic acid and the resulting mixture was subjected to reflux. This study centered on a diverse set of NDI and PDI ligands, comprising L‐ala‐NDI, B‐ala‐NDI, Gly‐NDI, Imi‐NDI, Pyr‐NDI, L‐ala‐PDI, B‐ala‐PDI, Gly‐PDI, Imi‐PDI, and Pyr‐PDI ligands. Crystal structures were obtained for three NDI ligands, while the characterization of all ligands involved several analytical techniques such as NMR, IR, UV, DFT, TD‐DFT calculations, and single‐crystal x‐ray crystallography specifically for the NDI ligands. The investigation focused on studying the electron acceptor/donor behavior of the NDI and PDI ligands, identifying their potential for charge transfer applications. Furthermore, the NLO (nonlinear optical) response of all 10 NDI and PDI ligands was assessed through an analysis involving HOMO‐LUMO, TDM, EDDM, NCI, Iso‐surface, MEP, natural population, and DOS analysis. This evaluation encompassed the examination of linear polarizability, as well as first and second hyperpolarizability in the context of NLO. The findings of the study revealed that Gly‐PDI, Imi‐PDI, L‐ala‐PDI, and B‐ala‐PDI ligands displayed a higher NLO response compared with the other ligands. These results highlight the potential of these ligands for nonlinear optical applications. The comprehensive characterization and assessment of the NDI and PDI ligands contribute to a deeper understanding of their electron properties, positioning them as promising candidates for charge transfer and nonlinear optical materials.