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This perspective highlights advances in the preparation and understanding of metal nanoclusters stabilized by organic ligands with a focus on N-heterocyclic carbenes (NHCs). We demonstrate the need for a clear understanding of the relationship between NHC properties and their resulting metal nanocluster structure and properties. We emphasize the importance of balancing nanocluster stability with the introduction of reactive sites for catalytic applications and the importance of a better understanding of how these clusters interact with their environments for effective use in biological applications. The impact of atom-scale simulations, development of atomic interaction potentials suitable for large-scale molecular dynamics simulations, and a deeper understanding of the mechanisms behind synthetic methods and physical properties (e.g., the bright fluorescence displayed by many clusters) are emphasized.

Atomically precise hydrido gold nanoclusters are extremely rare but interesting due to their potential applications in catalysis. By optimization of molecular precursors, we have prepared an unprecedented N-heterocyclic carbene-stabilized hydrido gold nanocluster, [Au24(NHC)14Cl2H3]3+. This cluster comprises a dimer of two Au12kernels, each adopting an icosahedral shape with one missing vertex. The two kernels are joined through triangular faces, which are capped with a total of three hydrides. The hydrides are detected by electrospray ionization mass spectrometry and nuclear magnetic resonance spectroscopy, with density functional theory calculations supporting their position bridging the six uncoordinated gold sites. The reactivity of this Au24H3cluster in the electrocatalytic reduction of CO2is demonstrated and benchmarked against related catalysts.