A benzo-fused double [7]carbohelicene (D7H) was synthesized through a regioselective cyclodehydrogenation of a tetranaphthyl-p-terphenyl-based precursor. The twisted (D7H-1) and anti-folded (D7H-2) conformers of D7H were separated by recrystallization, and their double helicene structures with overlapping terminal benzene rings were unambiguously elucidated by X-ray crystallography. A record-high isomerization barrier (46.0 kcal mol ) in double helicenes was estimated based on density functional theory (DFT) calculation, which resulted in the excellent conformational stability of D7H. The physicochemical properties of D7H-1 and D7H-2 were investigated by UV/Vis absorption spectroscopy and cyclic voltammetry, displaying the variation of electronic structure upon conformational changes. The optical resolution of the racemic D7H-1 was carried out by chiral HPLC, offering enantiopure D7H-1-(P,P) and D7H-1-(M,M), which were further characterized by circular dichroism spectroscopy.

Chiral organic cages can assist enantio-selective supramolecular polymerization through a catalyzed assembly (catassembly) strategy, like chaperones assist the assembly of biomolecules.

We constructed a series of novel chiral molecular face-rotating polyhedra (FRP) from two 10,15-dihydro-5H-diindolo[3,2-a:3',2'-c]carbazole (triazatruxene) derivatives and trans-1,2-cyclohexane diamine, and investigated how facial interactions and the positions of substituents determine the diastereoselectivity and geometry of the final assemblies.