While extensive research has explored manipulating supramolecular chirality through internal and external factors, the specific solvation effect remains uncharted territory. This study synthesized ortho-functionalized pillar[5]arene (P[5]) derivatives Mn and Dn via thiol-Michael addition, characterizing them through spectroscopic and X-ray single-crystal analyses. Mn and Dn interacted with chiral amines, yielding significant circular dichroism (CD) responses. Intriguingly, the chiral induction exhibited pronounced specific solvation effects, where achiral alcohols either enhanced, attenuated, or reversed CD signals. Testing over 40 alcohols revealed correlations between the specific solvation effects and alcohol polarity and acidity. Molecular dynamics simulations unveiled that the alcohol interacted distinctly through hydrogen bonding, with one ion pair bonding up to four alcohol molecules. The Rp- and Sp-preference of the P[5] core could be altered by the number of bonded alcohols. This work uncovers the critical role of alcohol-specific solvation in ion pair-involved chiral assembly, pertinent for asymmetric ion-pairing catalysis and the use of alcohol additives in organic solvents.
