Energetic and Topological Supramolecular Study and Nucleation Mechanism Proposal of Halogenated Phenols

Abstract

AbstractIn this work, an energetic and topological supramolecular study of 10 different halogenated phenols, X−C6H4−OH (X=F, Cl, Br and I) in the ortho, meta, and para positions was carried out, except for X=Br, in ortho‐ and meta‐X‐phenols. Most compounds have a molecular coordination number (MCN) of fourteen. All intermolecular interactions were classified, and the robustness was evaluated. Strong intermolecular interactions such as O−H⋅⋅⋅O and π⋅⋅⋅π contributed half the energy of the cluster, although interactions considered weak as C−H⋅⋅⋅X and C−H⋅⋅⋅π reached 40 % in energetic contribution, as they revealed a greater number of occurrences. Additionally, these theoretical data of energy were correlated with experimental data of melting point and packing density revealing a notable trend. In almost all cases evaluating the same position, the higher the density, the higher the melting point and the higher the stabilizing energy. Finally, nucleation proposals were suggested for all compounds and revealed that six compounds needed three stages, while four compounds needed only two stages to promote the growth of the supramolecular structure in three directions.