Difluorinated Cyclohexanes: Energetics and Intra‐ and Intermolecular Interactions

Fluorinated cyclohexanes are essential building blocks for high‐performance molecules, including ion carriers and liquid crystals. This quantum‐chemical study evaluates the relative energies of all difluorinated cyclohexane isomers, highlighting key intramolecular interactions as thermodynamic modulators. The stability of 1,1‐difluorocyclohexane arises from an anomeric‐like n F → σ* CF interaction, despite FCF repulsion. Dipolar repulsion between CF bonds affects isomers like diequatorial trans ‐1,2 and diaxial cis ‐1,3, while axial CH···CF electrostatic attraction stabilizes trans ‐1,3 and diaxial trans ‐1,4 isomers. Hyperconjugation involving antiperiplanar CH and CF bonds also contributes. Notably, diaxial CF bonds facilitate self‐assembly via interactions between negatively charged fluorines and positively charged hydrogens. This study advances understanding of fluorinated cyclohexanes’ thermodynamic behavior, providing a framework for designing tailored fluorinated compounds for advanced applications.