Chiral assembly of atomically precise metal nanoclusters

Abstract

The chiral assembly of atomically precise nanoclusters (NCs) into hierarchical superstructures is an emerging frontier that enables the design of functional materials with tailored chiroptical, catalytic, and photonic performance. This review provides a systematic synthesis of recent advances, with emphasis on the relationships linking assembly strategies to enhanced properties and applications. Mechanistically, directional supramolecular interactions (e.g., hydrogen bonding, π-π stacking, halogen bonding) and coordination chemistry drive diverse architectures, including fibrous helical bands, single/double/multi-helical motifs, and extended frameworks. Chirality arises intrinsically from asymmetric NC cores or ligand environments, or is extrinsically induced by chiral linkers or counterions. Assembly-induced confinement and anisotropic coupling suppress nonradiative decay pathways, thereby boosting photoluminescence (PL), circularly polarized luminescence (CPL), circularly polarized phosphorescence (CPP), and electrochemiluminescence (ECL). These enhancements underpin applications in circularly polarized light-emitting diodes (CP-LEDs), sensing, catalysis, and low-loss optical waveguides. We highlight a “structure-property-application" continuum, further informed by kinetic control, chiral amplification, and guest-responsive adaptive assembly. Finally, we outline key challenges and opportunities, including in situ mechanistic interrogation, exploration beyond coinage metals, and advanced directions in quantum optics and enantioselective technologies.