Improvement of theoretical UV–Vis spectra calculations by empirical solvatochromic parameters: Case study of 5-arylazo-3-cyano-1-ethyl-6-hydroxy-4-methyl-2-pyridones

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Molecular and biomolecular spectroscopy, 2022-05, Vol.272, p.120978, Article 120978
• Main Authors: Lađarević, Jelena M., Božić, Bojan Đ., Vitnik, Vesna D., Matović, Luka R., Mijin, Dušan Ž., Vitnik, Željko J.
• Format: Article
• Language: English
• Subjects: Azo dye; DFT calculation; Linear solvation energy relationship; Pyridone; Solvatochromism; UV–Vis spectra prediction
• ISSN: 1386-1425
• DOI: 10.1016/j.saa.2022.120978

[Display omitted] •Theoretical and experimental study of solvatochromism of pyridone dyes is performed.•LSER models used for quantification of intermolecular solvent–solute interactions.•Benchmark of 4 common DFT methods for the study of solvent effects on λmax is done.•New polylinear equations for more accurate prediction of UV–Vis maxima developed.•Empirical solvent parameters are used as additive corrections of solvent effects. In order to improve the performance of theoretical UV–Vis spectra predictions, a theoretical and experimental study of solvatochromic properties of ten azo pyridone dyes has been performed. For quantitative estimation of intermolecular solvent–solute interactions, a concept of the linear solvation energy relationships has been applied using Kamlet-Taft and Catalán models. Theoretical UV–Vis spectra for all dyes have been calculated using four TD-DFT methods in nine different solvents with the aim to define the most reliable model. Finally, new polylinear equations for more accurate theoretical prediction of UV–Vis maxima are developed using empirical Kamlet-Taft and Catalán solvent parameters as additive corrections for specific and nonspecific solvent–solute interactions.