Solvent Influence on Absorption Spectra and Tautomeric Equilibria of Symmetric Azomethine‐Functionalized Derivatives: Structural Elucidation and Computational Studies

Abstract

A new series of azomethine‐functionalized compounds was synthesized from the condensation of 2‐hydroxy‐1,3‐propanediamine and 2‐thienylcarboxaldehydes in the presence of a drying agent. The derivatives were spectroscopically characterized by NMR, LC‐MS, UV/Vis, IR and elemental analysis. Variable temperature 1H‐NMR (−60 to +60 °C) was performed to investigate the effect of solvent polarity; the capability of solvent to form H‐bond was found to dramatically influencing the tautomerization process of the desired structures. The calculated thermochemical parameters (ΔH298, ΔG298 and ΔS298) at DFT and MP2 levels of theory explained that 3 b exists in equilibrium with two tautomers. The basis of the electronic absorptions was pursued through Time‐Dependent Density‐Functional Theory (TD‐DFT). Analysis of the structural surfaces was inspected and the molecular electrostatic potential (MEP) demonstrated that the three functionalized compounds were relatively analogous in the electronic distributions. Furthermore, the electrophilic and nucleophilic centers lying on the molecular surfaces were probably playing a key‐role in stabilizing the compounds through the nonclassical C−H⋅⋅⋅π interactions and hydrogen bonding. The impact of solvent polarity on absorption spectra were investigated via solvatochromic shifts. For instance, compound 3 c displayed a gradual shift of the maximum absorption to the red area when the solvent polarity was increased, recording a 21 nm of bathochromic shift. In contrast, no significant solvent‐effect on 3 a and 3 b was observed. The solvation relation was pursued between Gutmann's donicity numbers the experimental λmax; exhibited almost positive linear performance with a minor oscillation, that ascribe to the possible weak interface between the molecules of solute and designated solvents. The bandgap energy of all products were assessed experimentally using optical absorption spectra following Tauc approach, giving −4.050 (3 a), −3.900 (3 b) and −3.210 (3 c) eV. However, the ΔE were computationally figured out from TD‐DFT simulation to be −4.258 (3 a), −4.022 (3 b) and −3.390 (3 c) eV.

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“…Solvatochromism is typically taken into account for these purposes in order to examine the impact of solvents on maximum absorption and to estimate the ground and excited states. [37] Negative solvatochromism (hypsochromic shift) results from the ground state, which is more stable in less polar solvents than the excited state. In contrast, the excited state exhibits positive solvatochromism (bathochromic shift) and is comparatively stronger in more polar solvents.…”

“…The molecular orbitals of the molecule get involved in the electronic absorption, which is driven to alter its absorption maximum. Solvatochromism is typically taken into account for these purposes in order to examine the impact of solvents on maximum absorption and to estimate the ground and excited states [37] . Negative solvatochromism (hypsochromic shift) results from the ground state, which is more stable in less polar solvents than the excited state.…”