Aromaticity in Semi-Condensed Figure-Eight Molecules.

Electron delocalization and aromaticity was comparatively evaluated in recently synthesized figure-eight molecules made of two condensed U-shaped polycyclic aromatic hydrocarbon moieties connected either by two single bonds or by two para-phenylene groups. The selected examples include molecules that incorporate eight-membered and sixteen-membered rings, as well as a doubly [5]helicene-bridged (1,4)cyclophane. We probe whether some electron delocalization could occur through the stereogenic single bonds in these molecules: Is aromaticity purely (semi-)local, or possibly also global in these molecules? It was concluded that the situation can go from a purely (semi-)local character when the dihedral angle at the connecting single bonds is large, such as in biphenyl, to a predominantly (semi-)local character with a minor global contribution when the dihedral angle is small, such as in the para-phenylene connectors of the [5] helicene-bridged cyclophane.