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

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

doi:10.24959/ophcj.20.189458

Authors

Tatyana S. Zhuk National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Ukraine https://orcid.org/0000-0001-5184-704X
Svetlana V. Lanovenko National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Ukraine
Oleksandr Ye. Pashenko National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Ukraine https://orcid.org/0000-0002-6240-2465
Andrey A. Fokin National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Ukraine https://orcid.org/0000-0001-9349-1619

DOI:

https://doi.org/10.24959/ophcj.20.189458

Keywords:

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

Abstract

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

Supporting Agency

the budget theme of the Ministry of Education and Science of Ukraine No. 0117U003854

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