Self-assembly of chiroptical ionic co-crystals from silver nanoclusters and organic macrocycles

Abstract

Atomically precise nanoclusters can be assembled into ordered superlattices with unique electronic, magnetic, optical, and catalytic properties. The co-crystallization of nanoclusters with functional organic molecules provides opportunities to access an even wider range of structures and properties but can be challenging to control synthetically. Here, we introduce a supramolecular approach to direct the assembly of atomically precise Ag nanoclusters into a series of nanocluster‒organic ionic cocrystals (NOICs) with tunable structures and properties. By leveraging non-covalent interactions between anionic Ag nanoclusters and cationic organic macrocycles with tunable sizes, the orientation of nanocluster surface ligands can be manipulated to achieve in-situ resolution of enantiopure NOICs that feature large chiroptical effects. Beyond chirality, this cocrystal assembly approach provides a promising platform for designing functional solid-state nanomaterials through a combination of supramolecular chemistry and atomically precise nanochemistry.