Solubility-Driven Isolation of a Metastable Nonagold Cluster with Body-Centered Cubic Structure.

The conventional synthetic methodology for atomically precise gold nanoclusters by using reduction in solution offers only the thermodynamically most stable nanoclusters. Herein, a solubility-driven isolation strategy is reported to access a metastable gold cluster. The cluster, with the composition of [Au (PPh ) ] (1), displays an unusual, nearly perfect body-centered cubic (bcc) structure. As revealed by ESI-MS and UV/Vis measurements, the cluster is metastable in solution and converts to the well-known [Au (PPh ) Cl ] (2) within just 90 min. DFT calculations revealed that although both 1 and 2 are eight-electron superatoms, there is a driving force to convert 1 to 2 as shown by the increased cohesion and larger HOMO-LUMO energy gap of 2. The isolation and crystallization of the metastable gold cluster were achieved in a biphasic reaction system in which reduction of gold precursors and crystallization of 1 took place concurrently. This synthetic protocol represents a successful strategy for investigations of other metastable species in metal nanocluster chemistry.