Structural and solvent effects on the spectroscopic properties of 1, 8‐naphthalimide derivatives: A density functional study

The molecular structures of 1, 8‐naphthalimide derivatives were investigated at density functional theory level within framework of PBE1PBE/6‐31G*. The vertical ionization potential and their delocalization energy of the X‐ray solid structure and gas‐phase optimized structure were explored. The configuration difference between them was attributed to the π‐π interaction of the solid effect, which has negligible effect on their absorption spectra. Solid effect also weakens the intramolecular interaction. Their absorption and luminescent spectra in gas and solvent phase were calculated by time‐dependent density functional theory (TDDFT) and conductor polarizable continuum models (CPCM)‐TDDFT approaches. Obvious red shifts from the solvent effect were found. Substituents on the imides will not improve their spectra properties a lot, whereas substituents on the naphthalene of naphthalimide would modify their properties to emit different spectra. Systematical deviation of vertical excitation energy from absorption and emission spectra, obtained by CPCM‐PBEPBE/6‐31G* and CIS‐CPCM‐PBEPBE/6‐31G* models, were about 0.05 eV and 0.02 eV compared with the experimental values. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011