Perfluoroaromatic Bisselanes: From Molecular Design to Supramolecular Architecture Through Tandem σ/π-hole...

The molecular design of a series of perfluoroarylbisselanes (30-68 %) o-, m- and p-(Ar^FSe)₂C₆F₄ and (Ar^FSe)₂C₁₂F₈ (Ar^F=C₆F₅ and p-C₆F₄CF₃) were achieved through the reaction of Ar^FSeCu with diiodoperfluoroarenes bearing phenyl and biphenyl rings. Analysis of the X-ray diffraction (XRD) data for the resulting perfluoroaromatic bisselanes 5-12 demonstrated their significant potential for constructing supramolecular architectures through tandem noncovalent interactions, including chalcogen bonding (ChB) and π_hole-π interactions. 1,2-Bis(pentafluorophenylseleno)tetrafluorobenzene 5 was cocrystallized with dibenzyl ether, yielding the adduct 5₂⋅Bn₂O, which exhibited a triad structural motif. Its XRD data provided structural insights into the ChB-based catalysis mechanism of Friedel-Crafts type reaction involving benzyl ether derivatives. Comprehensive density functional theory studies: energy decomposition analysis (EDA), molecular electrostatic potential (MEP) assessments, van der Waals potential evaluations, electrostatic potential and energy density (ED/ESP) plots, as well as natural bond orbital (NBO) analysis - revealed that Se⋅⋅⋅O chalcogen bonding (10.1 kcal/mol) and π_hole-π interactions (12.6 kcal/mol) contribute comparably to the overall energetics, thus playing a significant role in guiding molecular assembly.