The partial fluorination of polycyclic aromatic hydrocarbons often produces a layered crystal packing, where fluorinated aromatic surfaces are stacked over nonfluorinated aromatic surfaces. Herein, we report the synthesis and crystal packing of partially fluorinated [4]helicenes with steric congestion resulting from H and F atoms in the fjord region. F6 -[4]Helicene forms head-to-tail columnar stacks consisting of an alternate arrangement of perfluorinated and nonfluorinated naphthalene moieties. With decreasing fluorine content, aromatic stacking switched from arene-fluoroarene (ArH -ArF ) hetero-stacking to ArH -ArH /ArF -ArF homo-stacking with the help of intermolecular C-H⋅⋅⋅F contacts in the fjord region. As a result, head-to-head columnar stacks appear. Therefore, the conventional ArH -ArF stacking motif is not always applicable to Fn -[4]helicenes with twisted π-surfaces.
Keywords: Arene; Fluorine; Helical structures; Noncovalent interactions; Pi interactions.
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