Para halo, X = F, Cl, and Br, substitution effect on tautomerism, keto-enol content, molecular structure, intramolecular hydrogen bonding, and enol-enol equilibrium constants of 4,4,4-trifluoro-1-phenyl-1,3-butanedione, known as trifluorobenzoylacetone (TFBA), have been investigated by means of density functional theory calculations and NMR, IR, and UV–Vis spectroscopic methods. Comparing the calculated and experimental results suggests coexisting of two stable cis-enol forms of titled molecules in comparable proportions in the sample. The theoretical and experimental results show that the equilibrium constants between both stable cis-enol forms of the studied molecules are similar, about 1.1–1.2. According to the AIM calculated results performed at the B3LYP/6-311++G∗∗ level, the target para halo molecules have a hydrogen bond strength of about 18.6 kcal/mol, as a medium hydrogen bond, similar to that of TFBA. The theoretical and experimental results indicate that there is no considerable difference between the hydrogen bond strength of the X-substituted titled molecules.

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