This research provides information about combinations of several amino acids, including l-proline (Pro), l-arginine (Arg), and l-histidine (His), with phenoxyacetic acid herbicides (MCPA and 2,4-D). Five amino acid ionic liquids (AAILs), one amino acid higher-melting salt (AAHMS), and two amino acid liquid cocrystals (AALCs) were obtained in high yields (>90%). The ionization of the six new structures was confirmed by NMR, IR, and molecular modeling. X-ray crystallography was used to definitively confirm the binding location of the mobile hydrogen. Furthermore, we propose a computational method for estimating the energy of specific hydrogen bond(s) in AAIL crystals based on the NBO and QTAIM hydrogen bond parameters obtained by model calculations. An in-depth analysis of the structures allowed to answer the question posed in the title, ionic liquids or liquid cocrystals? AAILs based on arginine and histidine were obtained. In contrast, combining proline with MCPA and 2,4-D led to AALCs. Finally, the compounds were analyzed to measure their herbicidal activity. These studies proved that the novel form of MCPA or 2,4-D improved its ability to control weeds compared to commercial formulations containing the same active ingredients.
Keywords: amino acids; biological activity; crystallography; herbicidal ionic liquids; molecular modeling.