Heterochiral Diastereomer-Discriminative Diphanes That Form Hierarchical Superstructures with Nonlinear Optical Properties.

In order to study the emergence of homochirality during complex molecular systems, most works mainly concentrated on the resolution of a pair of enantiomers. However, the preference of homochiral over heterochiral isomers has been overlooked, with very limited examples focusing only on noncovalent interactions. We herein report on of twin-cavity cages (denoted as ) against heterochiral tris-(2-aminopropyl)amine (TRPN) bearing triple stereocenters. This results from distinct spatial orientation of reactive secondary amines on TRPN. Homochiral TRPNs with all reactive moieties rotating in the same way facilitate the formation of homochiral and achiral with low strain energy, while heterochiral TRPNs with uneven orientation of secondary amines preclude the formation of cage-like entity, since the virtual exhibit considerably high strain. Moreover, homochiral self-assemble into an acentric superstructure composed of single-handed helices, which exhibits interesting nonlinear optical behavior. Such a property is a unique occurrence for organic cages, which thus showcases their potential to spawn novel materials with interesting properties and functions.