Atomically Precise Rod-Like Au₂₅ Nanoclusters: A Platform for Property Modulation via Ligand Engineering and Heterometal Doping

Atomically precise gold nanoclusters are highly attractive owing to their well-defined structures, which enable detailed elucidation of structure–property relationships at the molecular level. Among them, rod-like Au₂₅ nanoclusters have emerged as a representative system due to their high structural stability and tunable metal–ligand interfacial interactions. This review provides a unified perspective on rod-like Au₂₅ nanoclusters, encompassing key characterization methods, ligand engineering strategies, heteroatom doping effects, and future research directions. Current studies reveal that ligand engineering primarily governs low-energy electronic transitions, near-infrared emission, chiroptical responses, and substrate-activation pathways by modulating shell rigidity, local asymmetry, and site exposure. In contrast, heterometal doping regulates photoluminescence behavior, energy-transfer processes, and photocatalytic and electrocatalytic performance through site-selective substitution, thereby reshaping frontier-orbital distributions, energy-level alignment, and interfacial electronic structure. Future progress will require advances in predictive synthesis, site-selective doping, operando characterization, and the integrated design of ligand engineering and heterometal doping within a single cluster platform. These developments are expected to further establish rod-like Au₂₅ nanoclusters as a versatile model system for understanding and controlling structure-function relationships in atomically precise nanomaterials.