N-Centered Chiral Self-Sorting and Supramolecular Helix of Tröger's Base-Based Dimeric Macrocycles in Crystalline State

Abstract

Three stereoisomers of Tröger's Base-based dimeric macrocycles Trögerophane <b>1</b> (<b>T1</b>) including one pair of enantiomers ( <b><i>rac</i>-T1</b>) and one meso isomer ( <b><i>R</i></b> _2<i>N</i> <b><i>S</i></b> _2<i>N</i> <b>-T1</b>) were obtained and fully characterized by X-ray analysis. In the crystalline stacking state <b><i>R</i></b> _2<i>N</i> <b><i>S</i></b> _2<i>N</i> <b>-T1</b> showed heterochiral self-sorting behavior along <i>a</i> axis with cofacial π<i>-</i>π stacking interactions, while <b><i>rac</i>-T1</b> showed heterochiral self-sorting behavior along <i>c</i> axis with slipped π-π stacking interactions, respectively. Meanwhile both of them showed homochiral self-sorting behavior along <i>b</i> axis as well as one pair of supramolecular helixes were formed in both cases. All the self-sorting behaviors are controlled by two chiral Tröger's Base units from neighboring molecules. To the best of our knowledge, such chiral self-sorting and supramolecular helixes of <i>N</i>-centered chiral superstructures is a rare example. In addition, <b><i>R</i></b> _2<i>N</i> <b><i>S</i></b> _2<i>N</i> <b>-T1</b> and <b><i>rac</i>-T1</b> demonstrated different adsorption capacities toward the vapor of dichloromethane and acetone, respectively.