Analysis of CF···FC interactions on cyclohexane and naphthalene frameworks

Area of Science:

• Organic Chemistry
• Computational Chemistry
• Chemical Physics

Background:

• Organofluorine compounds exhibit unique properties due to fluorine's high electronegativity.
• Understanding noncovalent interactions is crucial for predicting molecular behavior and reactivity.
• Intramolecular interactions involving fluorine atoms are of significant interest.

Purpose of the Study:

• To investigate intramolecular CF···FC interactions in various organofluorine molecules.
• To assess the applicability of the noncovalent interaction (NCI) method for identifying these interactions.
• To explore the relationship between CF···FC interactions and spin-spin coupling constants.

Main Methods:

• Computational modeling at the MP2/aug-cc-pVDZ level of theory.
• Application of the noncovalent interaction (NCI) method to analyze electron density.
• Analysis of optimized molecular geometries for selected organofluorine compounds.

Main Results:

• The NCI method identified all studied intramolecular CF···FC interactions as attractive.
• Attractive interactions were observed even in cases lacking clear energetic stabilization via isodesmic reactions.
• Potential correlations between CF···FC interactions and JFF spin-spin coupling constants were discussed.

Conclusions:

• The NCI method is effective in detecting attractive intramolecular CF···FC interactions.
• These interactions contribute to the structural and electronic properties of organofluorine compounds.
• Further investigation into the link between these interactions and spectroscopic properties is warranted.