Surface Coordination of Multiple Ligands Endows N‐Heterocyclic Carbene‐Stabilized Gold Nanoclusters with High Robustness and Surface Reactivity

Abstract Deciphering the molecular pictures of the multi‐component and non‐periodic organic‐inorganic interlayer is a grand technical challenge. Here we show that the atomic arrangement of hybrid surface ligands on metal nanoparticles can be precisely quantified through comprehensive characterization of a novel gold cluster, Au 44 ( i Pr 2 ‐bimy) 9 (PA) 6 Br 8 ( 1 ), which features three types of ligands, namely, carbene (1,3‐diisopropylbenzimidazolin‐2‐ylidene, i Pr 2 ‐bimy), alkynyl (phenylacetylide, PA), and halide (Br), respectively. The delicately balanced stereochemical effects and bonding capabilities of the three ligands give rise to peculiar geometrical and electronic structures. Remarkably, despite its complex and highly distorted surface structure, cluster 1 exhibits unusual catalytic properties and yet it is highly stable, both chemically and thermally. Moreover, rich reactive sites on the cluster surface raise the prospect of bio‐compatibility (as it can be functionalized to yield water‐soluble derivatives) and bio‐applications.