Rapid Conversion of a Au 9 Ag 12 into a Au x Ag 16‐x Nanocluster via Bisphosphine Ligand Engineering

The [Aux Ag16-x (SAdm)8 (Dppe)2 ] nanocluster with aggregation-induced emission (AIE) was synthesized from a non-fluorescent [Au9 Ag12 (SAdm)4 (Dppm)6 Cl6 ](SbF6 )3 nanocluster via a ligand-exchange engineering (Dppe=1,2-Bis(diphenylphosphino)ethane, Dppm=Bis(diphenylphosphino)methane, HSAdm=1-Adamantanethiol). The nanocluster has a Au-doped icosahedral Aux Ag13-x core, capped by two Ag(SR)3 , one Ag(SR)2 and two Dppe ligands. By changing the achiral Dppe ligand into a chiral dbpb ligand ((2S,3S)-(-)-Bis(diphenylphosphino)butane or (2R,3R)-(+)-2,3-Bis(diphenylphosphino)butane), chiral nanoclusters are obtained. ESI-MS and UV-vis spectroscopy were performed to track the reaction. This work provides guidance for the construction of new clusters by etching clusters with multidentate phosphine ligands.