The Cohesive Interactions in Phenylimidazoles.

Abstract

This work presents a comprehensive study exploring the thermodynamics of the solid phase of a series of phenylimidazoles, encompassing experimental measurements of heat capacity, volatility, and thermal behavior. The influence of successive phenyl group insertions on the imidazole ring on thermodynamic properties and supramolecular behavior was thoroughly examined through the evaluation of 2-phenylimidazole (2-PhI), 4-phenylimidazole (4-PhI), 4,5-diphenylimidazole (4,5-DPhI), and 2,4,5-triphenylimidazole (2,4,5-TPhI). Structural correlations between molecular structure and thermodynamic properties were established. Furthermore, the investigation employed UV-vis spectroscopy and quantum chemical calculations. Additive effects arising from the introduction of phenyl groups were found through the analysis of the solid-liquid and solid-gas equilibria, as well as heat capacities. A good correlation emerged between the thermodynamic properties of sublimation and the molar volume of the unit cell, evident across 2-PhI, 4,5-DPhI, and 2,4,5-TPhI. In contrast to its isomer 2-PhI, 4-PhI exhibited greater cohesive energy due to the stronger N-H···N intermolecular interactions, leading to the disruption of coplanar geometry in the 4-PhI molecules. The observed higher entropies of phase transition (fusion and sublimation) are consistent with the higher structural order observed in the crystalline lattice of 4-PhI.