Intramolecular π-π Interactions in Flexibly Linked Partially Fluorinated Bisarenes in the Gas Phase

Abstract

Three compounds with phenyl and pentafluorophenyl rings bridged by (CH₂ )₃ and (CH₂ )₂ SiMe₂ units were synthesized by hydrosilylation and C-C coupling reactions. Their solid-state structures are dominated by intermolecular π stacking interactions, primarily leading to dimeric or chain-type aggregates. Analysis of free molecules in the gas phase by electron diffraction revealed the most abundant conformer to be significantly stabilized by intramolecular π-π interactions. For the silicon compounds, structures characterized by σ-π interactions between methyl and pentafluorophenyl groups are second lowest in energy and cannot be excluded completely by the gas electron diffraction experiments. C₆ H₅ (CH₂ )₃ C₆ F₅ , in contrast, is present as a single conformer. The gas-phase structures served as a reference for the evaluation of a series of (dispersion-corrected) quantum-chemical calculations.

Keywords: bridged arenes; dispersion interactions; gas electron diffraction; intermolecular π stacking; intramolecular π stacking.