Structures, Energetics, and Spectra of (NH) and (OH) Tautomers of 2-(2-Hydroxyphenyl)-1-azaazulene: A Density Functional Theory/Time-Dependent Density Functional Theory Study

Abstract

Tautomerization of 2-(2-hydroxyphenyl)-1-azaazulene (2OHPhAZ) in the gas phase and ethanol has been studied using B3LYP, M06-2X, and ωB97XD density functional theory (DFT) with different basis sets. For more accurate data, energies were refined at CCSD(T)/6-311++G(2d,2p) in the gas phase. Nuclear magnetic resonance (NMR), aromaticity, Fukui functions, acidity, and basicity were also calculated and compared with experimental data. Time-dependent density functional theory (TDDFT)-solvation model based on density (TDDFT-SMD) calculations in acetonitrile have been utilized for the simulation of UV–vis electronic spectra. In addition, electronic structures of the investigated system have been discussed. The results reveal that the enol form (2OHPhAZ) is thermodynamically and kinetically stable relative to the keto tautomer (2OPhAZ) and different rotamers (2OHPhAZ–R1:R3) in the gas phase and ethanol. A comparison with the experiment illustrates a good agreement and supports the computational findings.