The Metal Coordination Effects on the Optoelectronic Properties of Perylene Diimide and Nucleotide Supramolecular Complex (GMP:PDI: Ag(I)/Co(II)/Zn(II)): Computational and Experimental Studies

In this comprehensive investigation, we present an integrated computational and experimental study of a series of metal-doped supramolecular PDI(β-ala)-GMP complexes using Ag(I)/Co(II)/Zn(II) as central metal ions. The supramolecular assemblies were critically analyzed in terms of optoelectronic properties and electronic behaviors. High-order computational studies, such as noncovalent interaction (NCI) and reduced density gradient (RDG) isosurface mapping, electron density difference maps (EDDM), Hirschfeld surface analysis, and frontier molecular orbital (FMO) theory, gave a more in-depth insight into the electronic structure, charge transfer, and the intermolecular interactions. Additionally, stability indices, natural bond order (NBO) analysis, dipole moment measurements, and full optoelectronic property calculations were done to rationalize structure–property relationships. The formation and stability of the metal-doped supramolecular architectures were experimentally validated by the use of spectroscopic (ultraviolet–visible (UV–vis), Fourier transform infrared (FTIR), and nuclear magnetic resonance (NMR)) and structural (PXRD) methods. It is important to note that Zn 2 PDI(GMP) 2 (H 2 O) 4 complex exhibited a better electronic delocalization and strong intermolecular interactions, thereby making it one of the most promising products in the next-generation photonic and optoelectronic applications. This work provides the design principles of engineering supramolecular materials with the desired optoelectronic properties that lie between computational predictions and experimental assembly.