Programmed Negative Allostery with Guest-Selected Rotamers Control Anion-Anion Complexes of Stackable Macrocycles

摘要

A new rotamer-based strategy for negative allostery has been used to control host–host interactions and product yield upon anion complexation. Coassembly of anion dimers as guests inside two cyanostar macrocycles drives selection of one rotamer in which all ten steric groups get directed outward to destabilize triply stacked macrocycles. A large entropy penalty (ΔS ) is quantified upon anion binding when the multiple dynamic rotamers collapse down to one.