Probing Self‐Assembly of Ammeline in Chloroform and Aqueous Media: Interplay Between Hydrogen Bonding Diversity and Dimerization

Abstract

AbstractAmmeline (AM) is a molecule with a very low reputation in the field of supramolecular community, but with a recently proven potential both experimentally and theoretically. In this work, dispersion‐corrected density functional theory (DFT‐D) computations and molecular dynamics (MD) simulations were employed to understand the aggregation mechanism of AM in chloroform and water media. Our DFT‐D and MD analyses show that the most important interactions are those formed by the amine groups (−NH2) with both the pyridine‐type nitrogen atoms and the carbonyl groups (C=O). In the more polar solvent, the interactions between water molecules and the C=O group prevent the AM from forming more interactions with itself. Nevertheless, four types of dimers involving N−H ⋅ ⋅ ⋅ O interactions were found to exist in water solutions. The overlooked tetrel bond between endocyclic N and C atoms can also stabilize dimers in solution. Moreover, while most AM dimers are enthalpy‐driven, our results indicate that the unique DD‐AA dimer (D=donor, A=acceptor) that originates cyclic rosettes is entropy‐driven.