Tuning electrochemical properties of ultra-small gold nanoclusters: Insights from phosphine and Di-N-heterocyclic carbene ligands

The metal-ligand interface in monolayer-protected metal nanomaterials plays a critical role in determining their overall characteristics. In this framework, atomically precise nanoclusters represent an ideal model to rationalize structure-properties correlations. Herein we explore the electrochemical behavior of novel Au11 and Au13 nanoclusters (NCs) protected by phosphines (PR3) and di-N-heterocyclic carbene (di-NHCs) ligands. By modulating di-NHC functionalization and exploring various substitution patterns on the carbene backbone, we gain insight into how ligands affect the electrochemical properties of these nanosystems. This approach allows us to establish structure-property relationships, illuminating the complex interplay between ligand design and the resulting electrochemical behavior of Au NCs. Computational results support the overall picture of the ability to fine-tune potential shifts through targeted modifications of di-N-heterocyclic carbenes within the metal NC monolayer, which holds significant promise for a wide range of applications.