Identifying the Real Chemistry of the Synthesis and Reversible Transformation of AuCd Bimetallic Clusters.

The capability of precisely constructing bimetallic clusters with atomic accuracy provides exciting opportunities for establishing their structure-property correlations. However, the chemistry (the charge state of precursors, the property of ligands, the amount of dopant, and so forth) dictating the fabrication of clusters with atomic-level control has been a long-standing challenge. Herein, based on the well-defined Au 25 (SR) 18 cluster (SR = thiolates), we have systematically investigated the factors of steric hindrance and electronic effect of ligands, the charge state of Au 25 (SR) 18 , and the amount of dopant that may determine the structure of AuCd clusters. It is revealed that [Au 19 Cd 3 (SR) 18 ] - can be obtained when a ligand of smaller steric hindrance is used, while Au 24 Cd(SR) 18 is attained when a larger steric hindrance ligand is used. In addition, negatively charged [Au 25 (SR) 18 ] - is apt to form [Au 19 Cd 3 (SR) 18 ] - during Cd doping, while Au 24 Cd(SR) 18 is produced when neutral Au 25 (SR) 18 is used as a precursor. Intriguingly, the reversible transformation between [Au 19 Cd 3 (SR) 18 ] - and Au 24 Cd(SR) 18 is feasible by subtly manipulating ligands with different steric hindrances. Most importantly, by introducing the excess amount of dopant, a novel bimetallic cluster, Au 4 Cd 4 (SR) 12 is successfully fabricated and its total structure is fully determined. The electronic structures and the chirality of Au 4 Cd 4 (SR) 12 have been elucidated by density functional theory (DFT) calculations. Au 4 Cd 4 (SR) 12 reported herein represents the smallest AuCd bimetallic cluster with chirality.