An Ortho-Tetraphenylene-Based "Geländer" Architecture Consisting Exclusively of 52 sp2-Hybridized C Atoms

A new type of "Gelander" molecule based on a ortho-tetraphenylene core is presented. The central para-quaterphenyl backbone is wrapped by a 4,4'-di((Z)-styryl)-1,1'-biphenyl banister, with its aryl rings covalently attached to all four phenyl rings of the backbone. The resulting helical chiral bicyclic architecture consists exclusively of sp(2)-hybridized carbon atoms. The target structure was assembled by expanding the central ortho-tetraphenylene subunit with the required additional phenyl rings followed by a twofold macrocyclization. The first macrocyclization attempts based on a twofold McMurry coupling were successful but low yielding; the second strategy, profiting from olefin metathesis, provided satisfying yields. Hydrogenation of the olefins resulted in a saturated derivative of similar topology, thereby allowing the interdependence between saturation and physico-chemical properties to be studied. The target structures, including their solid-state structures, were fully characterized. The helical chiral bicycle was synthesized as a racemate and separated into pure enantiomers by HPLC on a chiral stationary phase. Comparison of recorded and simulated chiroptical properties allowed the enantiomers to be assigned.