Hierarchical Homochiral Assembly of Polyhedral Cage-Type Nanoclusters

Hierarchical chiral self -assembly is of profound significance for biomolecules for their biological functions. Atom -precise metal nanoclusters (NCs) offer better opportunities to construct hierarchical superlattices. Nevertheless, achieving hierarchical homochiral assembly of nanocrystals protected by achiral ligands has proven to be a formidable task, with existing examples primarily limited to heterochiral assembly. Here we put forward a hierarchical assembly strategy towards precisely fabricating highly ordered homochiral superstructures. First, clusterin-nanocage type copper -hydride NCs act as synthons, of which entity is featured with a hexagonal close -packed Cu9 kernel embedded in a C3 -symmetric trigonal-prismatic metallacage, leading to a chiral core -shell primary structure with either P or M conformation. Then four homochiral NCs combined with guests through synergistic noncovalent interactions spontaneously organize into a supramolecular tetrahedral secondary structure within a unit cell. Finally, these nanoscopic supramolecular motifs pack into tertiary hierarchical superlattice of chiral cubic crystalline phase. Additionally, the crystalline material shows excellent robustness, and fascinating blueexcitable near -infrared thermally activated delayed fluorescence behavior. This work not only exhibits that nanocage-type NCs can be smart as proteins to translate chiral primary structure into tertiary chiral hierarchical complexity, but also provides new insights into structure -to -superstructure, enabling bottom -up creation of higher -level hierarchical homochiral superlattice structures.