RESUMO
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.
RESUMO
Atomically precise gold nanoclusters (AuNCs) are interesting nanomaterials with potential applications in catalysis, bioimaging and optoelectronics. Their compositions and properties are commonly evaluated by various analytical techniques, including UV-vis spectroscopy, NMR spectroscopy, ESI mass spectrometry, and single-crystal X-ray diffraction. While these techniques have provided detailed insights into the structure and properties of nanoclusters, synthetic methods still suffer from a lack of in situ and real-time reaction monitoring methodologies. This limits insight into the mechanism of formation of AuNCs and hinders attempts at optimization. We have demonstrated the utility of HPLC-MS as a monitoring methodology in the synthesis of two NHC-protected gold nanoclusters: [Au13(NHC)9Cl3]2+ and [Au24(NHC)14Cl2H3]3+. Herein we show that HPLC coupled with mass spectrometry and 13C NMR spectroscopy of labelled derivatives enables new insight into critical reaction dynamics of AuNCs synthesis and rapid reaction optimization.
