Tribenzotriquinacene-Based Triscyclophanes: Intra- and Inter-WingC3v-Symmetrical Extension of the Bowl-Shaped Tribenzotriquinacene Core

The syntheses and structural properties of novel triscyclophanes that bear the rigid, bowl-shaped tribenzotriquinacene (TBTQ) core are reported. Condensation of the 2,3,6,7,10,11-hexakis(chloromethyl) derivative with catechols and 1,2-benzenedithiol gives rise to elongation of the three indane wings (intra-wing extension), whereas incorporation of resorcinol, hydroquinone, and 1,3- and 1,4-benzenedithiol units occurs by bridging the 3D bays of the TBTQ framework (inter-wing extension), yielding TBTQ-based cavitands. Constitutional and conformational details were studied by X-ray diffraction, VT-NMR spectroscopy, and molecular modeling. The bay-bridged TBTQ-based triscyclophanes bearing 1,3-dioxy-and 1,3-dithiophenylene units adopt globular and cone-like C-3-symmetrical shapes, respectively, with limited conformational flexibility. Baybridging by 1,4-dioxy- and 1,4-dithiophenylene units generates a more complanate coverage of the bowl face with even less conformational flexibility.