Computational study on optoelectronic properties of perylene diimide derivatives and their supramolecular complexes with guanosine monophosphate

The intermolecular reactivity and electronic structure in perylene diimide (PDI) have been found to be strongly affected by bay substitution. However, a comprehensive understanding of the combined influence of substituent chemistry and nucleotide binding on their optoelectronic characteristics remains insufficiently understood. This study applies density functional theory (DFT) to analyze five electron-donating and electron-withdrawing bay-substituted PDI derivatives and its supramolecular complexes with guanosine monophosphate (GMP). The findings indicate that stability, charge redistribution, and electronic interactions are dependent upon the substituent. PDI-2CN and its GMP complex have the smallest HOMO–LUMO gap, the strongest binding and the significant optoelectronic response. PDI-2Si and its complex, on the other hand, have weak interactions and minimal electronic rearrangement. Spectral and electrical studies show that GMP binding improves charge-transfer properties and gives the series unique structural and vibrational fingerprints. These findings elucidate the structure-property correlations that dictate PDI-GMP assemblies and designate PDI-2CN-GMP as a viable candidate for optical and bio-optoelectronic applications.