Stereoisomerism in Nanohoops with Heterogeneous Biaryl Linkages of <i>E/Z</i>- and <i>R/S</i>-Geometries

The stereochemistry of cycloarylene nanohoops gives rise to unique cyclostereoisomerism originating from hoop-shaped molecular shapes. However, cyclostereoisomerism has not been well understood despite the ever-increasing number of structural variants. The present work clarifies the cyclostereoisomerism of a cyclophenanthrenylene nanohoop possessing both <i>E/Z</i>- and <i>R/S</i>-geometries at the biaryl linkages. Involvement of the <i>R/S</i> axial chirality in the nanohoop leads to the deviation of the structure from a coplanar belt shape and allows for structural variations with 51 stereoisomers with <i>E/Z</i>- and <i>R/S</i>-geometries. Experimental investigations of the dynamic behaviors of the cyclophenanthrenylene nanohoop revealed the presence of two-stage isomerization processes taking place separately at the <i>E/Z</i>- and <i>R/S</i>-linkages. Consequently, despite the presence of <i>E/Z</i>-fluctuations, the <i>R/S</i> axial chirality resulted in a separable pair of enantiomers. The structural information reported here, such as geometric descriptors and anomalous dynamics, may shed light on the common structures of various nanohoops