Atomically Precise Metal Nanoclusters: Tailoring Properties through Doping and Ligand Modifications

Metals exhibit different properties when transitioning from the bulk to the nanoscale. These unique characteristics make metallic nanoparticles important for applications in catalysis, sensing, and other advanced technologies. Atomically precise metal nanoclusters (NCs) are a class of materials that bridge the gap between small molecules and bulk metals, offering molecule-like properties with unique electronic, optical, and catalytic features. However, the synthesis and broader application of NCs remain constrained by challenges such as knowledge gaps in understanding synthetic mechanisms, controlling synthetic parameters for reproducible syntheses, and tailoring their properties for specific functions. This dissertation addresses these challenges by employing two strategies: (i) doping NCs with heterometals to fine-tune their structural and electronic properties, and (ii) modifying their surface ligands to enhance stability, reactivity, and functionality. The work focuses on the design, synthesis, characterization, and application of metal NCs stabilized by ligands such as N-heterocyclic carbene (NHC), phosphine, carborane dithiol, and antimony-based ligands. These NCs exhibit exceptional catalytic performance in model chemical reactions, such as cyclohexane oxidation and nitrophenol reduction. By systematically studying how ligand environments and doping influence reactivity, this work bridges the gap between fundamental science and practical applications. These insights lay the groundwork for designing next-generation materials with precise and tunable properties for sustainable chemical processes.