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. 2023 Sep 5;13(38):26587-26603.
doi: 10.1039/d3ra05081e. eCollection 2023 Sep 4.

TD-DFT calculations, dipole moments, and solvatochromic properties of 2-aminochromone-3-carboxaldehyde and its hydrazone derivatives

Omima M I Adly  1 , Ali Taha  1 , Shery A Fahmy  1 , Magdy A Ibrahim  1
Affiliations

TD-DFT calculations, dipole moments, and solvatochromic properties of 2-aminochromone-3-carboxaldehyde and its hydrazone derivatives

Omima M I Adly et al. RSC Adv. .

Abstract

2-Aminochromone-3-carboxaldehyde (ACC) and its hydrazones (ACMHCA and ACMNPHTCA) with semicarbazide hydrochloride and N-phenylthiosemicarbazide were synthesized and characterized by elemental analysis and spectral studies. The solvatochromic behavior of the title compounds in various solvents showed distinct bathochromic shifts on going from nonpolar to polar solvents, suggesting intramolecular-charge-transfer (ICT) solute-solvent interactions. The ground and excited state dipole moments of ACC, ACMHCA, and ACMNPHTCA were determined experimentally by the solvatochromic shift method using the Bilot-Kawski, Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet functions, and a microscopic Reichardt's solvent polarity parameter (ENT). All the investigated molecules showed a substantial increase in the dipole moment upon excitation to the emitting state. The experimental results were generally consistent with the values obtained by the TD-DFT, B3LYP/6-311G++(d,p) method. Molecular electrostatic potential (MEP) mapping and natural charge and natural bonding orbital (NBO) analysis were performed and the results were discussed. The 1H NMR chemical shifts of the prepared compounds were simulated by the gage independent atomic orbital (GIAO) method and compared with their experimental chemical shift values. The biological activity data were correlated with the frontier molecular orbitals. The photovoltaic behavior of the title compounds showed there was sufficient electron injection.

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Conflict of interest statement

The authors declare that they have no conflict of interest.

Figures

Scheme 1
Scheme 1. Structural formulas of ACC, ACMHCA, and ACMNPHTCA.
Scheme 2
Scheme 2. Synthetic routes for the hydrazones ACMHCA and ACMNPHTCA.
Scheme 3
Scheme 3. Keto–enol tautomeric form of ACMHCA.
Scheme 4
Scheme 4. Thione-thiol tautomeric form of ACMNPHTCA.
Scheme 5
Scheme 5. Some 1H-NMR chemical shifts (ppm) of ACC and its hydrazones.
Scheme 6
Scheme 6. Tautomeric structures of ACC.
Scheme 7
Scheme 7. Tautomeric structures of ACMHCA.
Scheme 8
Scheme 8. Tautomeric structures of ACMNPHTCA.
Fig. 1
Fig. 1. Electronic absorption and emission spectra of ACC, ACMHCA, and ACMNPHTCA.
Fig. 2
Fig. 2. (a). Fluorescence spectra for ACC, ACMHCA, and ACMNPHTCA in DMF. (b) Fluorescence spectra for ACC in different solvents.
Fig. 3
Fig. 3. (a). Relation between νStokes shift (νa − νf) vs. F1. (b) Relation between (νa + νf)/2 vs. F3. (c) Relation between νStokes shift (νa − νf) vs. FB. (d) Relation between νStokes shift (νa − νf) vs. ENT.
Fig. 4
Fig. 4. Contour plots of the HOMO and LUMO of ACC, ACMHCA, and ACMNPHTCA obtained at the B3LYP/6-311G(dp) level of theory.
Fig. 5
Fig. 5. Schematic representation of the MEP surfaces of ACC, ACMHCA, and ACMNPHTCA.
See this image and copyright information in PMC

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