Calyx‐ and Tub‐Shaped Polydentate σ‐Hole Systems Revealing Intermolecular Chalcogene···π–Alkyne Interactions

Poly σ‐hole donors, i.e., molecules that contain more than one σ‐hole donating function, can interact through weak noncovalent interactions with molecules that have regions of high electron density, like the lone pairs of anions, Lewis bases, and π‐systems. Therefore, such mono‐ and bidentate systems have been intensively studied in recent years and used in host‐guest chemistry and catalysis. Here we present the synthesis of tri‐, tetra‐, and hexadentate systems with CCSb(C 2 F 5 ) 2 and CCSeCF 3 functions using tin‐element exchange reactions. These systems are based on both the calyx‐shaped hexadehydrotribenzo[12]annulene and the tub‐shaped dibenzo[ a , e ]cyclooctatetraene. The molecular structure of the tub‐shaped systems shows inter‐ and intramolecular contacts related to the interaction of the σ‐holes with the electron‐rich fluorine and alkyne functions.