Hierarchical Engineering of Atomically Precise Gold Nanoclusters from Alloying to Cluster-Assembled Frameworks

Abstract Atomically precise gold nanoclusters (Au NCs) provide molecular-level platforms for understanding how atomic structure influences catalytic, photophysical, chiral, and electronic properties. Although alloying, ligand/interface engineering, and nanocluster assembly have each emerged as powerful approaches for tailoring Au NC function, they are often considered as separate design strategies. In this perspective, we organize recent advances in Au NC design across three interconnected levels of structural control: core alloying, ligand/interface engineering, and cluster-assembled materials. We discuss how alloying modifies the intrinsic electronic structure of the NC core, how ligand and interface engineering regulate the expression of these properties through electronic and structural control, and how coordination-mediated assembly organizes individual NCs into aggregates, superstructures, and crystalline frameworks with collective photophysical and electronic properties. By connecting these design strategies, this perspective provides a hierarchical view of Au NC design that links molecular precision to materials-level functionality and highlights opportunities for catalysis, sensing, optoelectronics, and nanoelectronics.