A Fused [5]Helicene Dimer with a Figure-Eight Topology: Synthesis, Chiral Resolution, and Electronic Properties

Chiral shape-persistent molecular nanocarbons are promising chiroptical materials; their synthesis, however, remains a big challenge. Herein, we report the facile synthesis and chiral resolution of a double-stranded figure-eight carbon nanobelt 1 in which two [5]helicene units are fused together. Two synthetic routes were developed, and, in particular, a strategy involving Suzuki coupling-mediated macrocyclization followed by Bi(OTf)(3)-catalyzed cyclization of vinyl ether turned out to be the most efficient. The structure of 1 was confirmed by X-ray crystallographic analysis. The isolated (P,P)- and (M,M)- enantiomers show persistent chiroptical properties with relatively large dissymmetric factors (|g(abs)|=5.4x10(-3) and |g(lum)|=1.0x10(-2)), which can be explained by the effective electron delocalization along the fully conjugated belt and the unique D-2 symmetry. 1 exhibits local aromatic character with a dominant structure containing eight Clar's aromatic sextet rings.