Isomeric forms of 1,4-dioxane in a microsolvation environment

Abstract

This study involves, for the first time, the comparative investigation of intermolecular interactions of the chair, 1,4 twist-boat, and 2,5 twist-boat conformations of 1,4-dioxane molecule within a microsolvation environment. In this context, the hydrogen bonding properties of binary, ternary and quaternary complexes involving the chair, 1,4 twist-boat, and 2,5 twist-boat conformations of the 1,4-dioxane molecule with water have been investigated by ab initio calculations. The ABCluster global search method in conjunction with the DFT level calculations has been utilized in this study to investigate the potential energy surfaces of 1,4-dioxane…(water)n (n = 0–3) clusters. The lowest relative energies of 1,4-dioxane-(water)n (n = 0–3) clusters are observed when the 1,4-dioxane molecule adopts the chair conformation, indicating its highest stability. However, it has been noted that structures in which the dioxane molecule is in the 2,5 twisted-boat conformation exhibit larger hydrogen bond energies. This observation suggests a notable impact of hydrogen bonding on the preferred molecular conformation. Furthermore, the relative energy differences between the conformers of 1,4-dioxane are influenced by the presence of water molecules in the system.