Macrocycle-Nanoclay Coassembly with Modulable Supramolecular Chirality Indicated by Surface Charges

Macrocyclic arenes with inherent or postmodified chirality are emerging supramolecular synthons in asymmetric sensing, recognition, organosynthesis, and chiroptical applications due to their cavity and inclusion phenomena. Herein, we explore the self-assembly of amino acid-conjugated heteroatomic calixarenes whose supramolecular chirality could be modulated by amino nanoclay. The macrocycles undergo self-assembly driven by anion recognition to transfer the chirality from amino acids to the supramolecular level, which depends on the structures of amino acids. The participation of aliphatic amine-grafted nanoclays disrupts individual anion recognition by the formation of electrostatic interaction pairs. The coassembly between macrocycles and nanoclay is accompanied by the evolution of supramolecular chirality, resulting in handedness inversion. The inverted supramolecular chirality, other than the chiroptical properties, can be indicated and monitored by surface charge and zeta potential in a high-fidelity manner. This work delicately utilizes switchable anion-recognition chemistry to establish a dynamic supramolecular chiral system, which sheds light on new protocols toward chiroptical sensing.