Interaction of a C–F Bond with the π-System of a CC Bond or “Head On” with a Proximate C–H Bond

We describe the synthesis and preliminary study of two molecules, in which a fluorine atom is positioned proximately above the π-orbitals of a CC bond or else wherein a C–F bond interacts in a “head on” fashion with a proximate C–H bond. The spectroscopic characteristics of these unusual interactions are documented, X-ray crystallographic analyses are reported, and theoretical calculations are employed to support the observed spectroscopy.