"First Come, First Served" and Threshold Effects in a Central-to-Planar-to-Helical Hierarchical Chiral Induction.

Perylene diimide tethered pillar[5]arene derivatives form aggregates in non-polar organic solvents, and the complexation of cationic amino acid ethyl ester (cAA-OEt) with the aggregates induce a central-to-planar-to-helical chirality transfer, leading to intensive circular dichroism (CD) signals having dissymmetric factors (g ) of up to 3.67×10 . The hierarchical chiral induction exhibited an intriguing threshold dose effect, namely, the chiral induction does not occur in the low concentration range of cAA-OEt but is triggered when cAA-OEt exceeds a threshold concentration. The inhibited interconversion between the Rp and Sp conformers of pillar[5]arene, which is further restricted in the aggregation, plays a crucial role in the threshold effect. When adding enantiopure cAA-OEt first to the threshold concentration and then adding an equal amount of the antipodal cAA-OEt to give cAA-OEt in racemic form, CD spectra having the same sign as the CD induced by first adding pure cAA-OEt were induced, thus showing an unprecedented "first come, first served" effect.