Luminescent properties of substituted 4-aminophthalimides: computations vs. experiment

Abstract

Luminescent properties of substituted 4-aminophthalimides: computations vs. experiment Aim. To perform a combined experimental and computational study on the luminescent properties of practically important class of organic dyes-4-aminophthalimides. Results and discussion. The absorption and fluorescence spectra of 4-aminophthalimide derivatives in polar protic and aprotic solvents were computed and matched vs. the experimental data. The changes in emission spectra are mainly related to the NH 2-group derivatization. The methyl substitution of amide hydrogen causes a batochromic shift of about 7 nm in the absorption peak and a negligible hypsochromic shift in the fluorescence peak, while introducing alkyl substituents to the amine moiety causes bathochromic shifts in absorption and emission peaks of 30-40 nm and 10-60 nm, respectively. Experimental part. Absorption and emission wavelengths were computed by the standard algorithm based on the ground state geometry optimization (equilibrium solvation), vertical excitation with nonequilibrium solvation, and the TD-DFT geometry optimization of the excited state structures. A reliable hybrid B3LYP functional was used in combination with DZ and TZ-quality basis sets. Conclusions. The computed absorption wavelengths are in excellent agreement with the experimental data and are only slightly solvent-dependent. At the same time, the discrepancy with the experiment for Stokes shifts reaches about 20 % at IEF-PCM-TD-B3LYP/6-31G(d). However, the general tendency for both absorption and fluorescence wavelengths is identical for all solvents within one molecule.