Tuning Intermolecular Interactions for Chiral Analysis: The Microwave Spectra and Molecular Structures of the Chiral Tag Candidates cis- and trans-2-Fluoro-3-(trifluoromethyl)oxirane and Their Gas-Phase Heterodimers with the Argon Atom

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 128; no. 43; pp. 9433 - 9446
• Main Authors: Leung, Helen O., Marshall, Mark D., Aucoin, Jordan M., Horowitz, Jonah R.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 31.10.2024
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.4c05830

The cis and trans isomers of the chiral tagging candidate molecule, 2-fluoro-3-(trifluoromethyl)­oxirane, as well as the lowest energy gas-phase heterodimer of each with the argon atom, are characterized via quantum chemistry calculations and microwave rotational spectroscopy from 5 to 18 GHz and their ground state, vibrationally averaged structures, are determined. Apart from the cis/trans nature of the ring substitution and small differences in the dihedral angle specifying the rotation of the trifluoromethyl group, the two oxirane molecules and their respective argon complexes each have remarkable structural similarity. In contrast, the binding mode of argon to the oxirane, while similar for the two complexes here, is distinct from those modes observed in previous argon-fluorooxirane species. The ability to tune the preferred mode of binding with differing levels of fluorine substitution may prove advantageous in applications of chiral tagging to a wide variety of analytes.