From Au11 to Au13: Tailored Synthesis of Superatomic Di-NHC/PPh3-Stabilized Molecular Gold Nanoclusters

Herein, we report a new method to synthesize molecular gold nanoclusters (AuNCs) stabilized by phosphine (PR3) and di-N-heterocyclic carbene (di-NHC) ligands. The interaction of di-NHC gold(I) complexes, with the general formula [(di-NHC)Au2Cl2] with well-known [Au11(PPh3)8Cl2]Cl clusters provides three new classes of AuNCs through a controllable reaction sequence. The synthesis involves an initial ligand metathesis reaction to produce [Au1 1(di-NHC) (PPh3)6Cl2]+ (type 1 clusters), followed by a thermally induced rearrange-ment/metal complex addition with the formation of Au13 clusters [Au13(di-NHC)2(PPh3)4Cl4]+ (type 2 clusters). Finally, an addi-tional metathesis process yields [Au13(di-NHC)3(PPh3)3Cl3]2+ (type 3 clusters). The electronic and steric properties of the employed di-NHC ligand affect the product distribution, leading to the isolation and full characterization of different clusters as the main product. A type 3 cluster has been also structurally characterized and was preliminarily found to be strongly emissive in solution