| Abstract: | The study of an enantiopure bicyclic pillar5]arene‐based molecular universal joint (MUJ) by single‐crystal X‐ray diffraction allowed for the first time the unequivocal assignment of the absolute configuration of a planar chiral pillar5]arene by circular dichroism spectroscopy. Crucially, the absolute configuration of the MUJ was switched reversibly by temperature, with an accompanying sign inversion of the anisotropy factor that varied by as much as 0.03, which is the largest value ever reported. Mechanistically, the reversible chirality switching of the MUJ is driven by the threading/dethreading motion of the fused ring and hence is dependent on both the size and nature of the ring and the solvent employed, reflecting the critical balance between the self‐complexation of the ring by pillar5]arene, the solvation to the excluded ring, and the inclusion of solvent molecules in the cavity. |
