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

Tatyana S. Zhuk, Svetlana V. Lanovenko, Oleksandr Ye. Pashenko, Andrey A. Fokin


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 NH2-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.


Received: 24.12.2019
Revised: 31.01.2020
Accepted: 27.02.2020


experimental luminescence spectra; absorption; fluorescence; Stokes shifts; 4-aminophthalimides; time-dependent density functional theory; polarizable continuum model

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Abbreviated key title: J. Org. Pharm. Chem.

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