Atomically Precise Rod‐Like Au ₂₅ 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 Au 25 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 Au 25 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 Au 25 nanoclusters as a versatile model system for understanding and controlling structure‐function relationships in atomically precise nanomaterials.