Abstract
Chiral molecular recognition is a pivotal phenomenon in biomolecular science, governed by subtle balances of intermolecular forces that are difficult to quantify. Non-covalent interactions involving aromatic moieties are particularly important in this realm, as recurring motifs in biomolecular aggregation. In this work, we use high-resolution broadband rotational spectroscopy to probe the dynamic conformational landscape enclosing the self-pairing topologies of styrene oxide, a chiral aromatic system. We reach a definite assignment of four homochiral and two heterochiral dimers using auxiliary quantum chemistry calculations as well as structure-solving methods based on experimental isotopic information. A complete picture of the dimer conformational space is obtained, and plausible routes for conformational relaxation are derived. Molecular structures are discussed in terms of conformational flexibility, the concerted effort of weak intermolecular interactions, and their role in the expression of the molecular fit.
Highlights
Chiral molecular recognition is a pivotal phenomenon in biomolecular science, governed by subtle balances of intermolecular forces that are difficult to quantify
We note that topologies comprising stacking of the oxirane unit with the phenyl ring were predicted, but those are much higher in energy (>10 kJ/mol) and were not considered further in this work
non-covalent interactions (NCI) surfaces will assist in the mapping of strong electrostatic, van der Waals and repulsive forces, and are here used to support our structural analysis and identification of contact points discussed
Summary
Chiral molecular recognition is a pivotal phenomenon in biomolecular science, governed by subtle balances of intermolecular forces that are difficult to quantify. Molecular recognition is a direct consequence of non-covalent interactions, generally resulting in contrasting differences in the 3D structures of homo- and heteroconfigurational aggregates6–10 These diastereomeric complexes differ in their stabilities, leading to chiral discrimination. Understanding the intricate balance between the intermolecular interactions at play during molecular aggregation is key to augment our knowledge of recognition processes at the molecular scale Relevant in this domain of chemical science are aromatic systems, given their abundance in biological environments as stabilisation units in larger macromolecular assemblies. Relevant in this domain of chemical science are aromatic systems, given their abundance in biological environments as stabilisation units in larger macromolecular assemblies11–14 In this framework, much effort has been put into understanding the structure and dynamics of the benzene dimer. Zehnacker-Rentien, Suhm and coworkers, and others have expanded these studies using UV-IR and Fourier transform infra-red spectroscopies
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