Controlling the Atomic Structure of Au30 Nanoclusters by a Ligand‐Based Strategy

Abstract We report the X‐ray structure of a gold nanocluster with 30 gold atoms protected by 18 1‐adamantanethiolate ligands (formulated as Au 30 (S‐Adm) 18 ). This nanocluster exhibits a threefold rotationally symmetrical, hexagonal‐close‐packed (HCP) Au 18 kernel protected by six dimeric Au 2 (SR) 3 staple motifs. This new structure is distinctly different from the previously reported Au 30 S(S‐ t Bu) 18 nanocluster protected by 18 tert ‐butylthiolate ligands and one sulfido ligand with a face‐centered cubic (FCC) Au 22 kernel. The Au 30 (S‐Adm) 18 nanocluster has an anomalous solubility (it is only soluble in benzene but not in other common solvents). This work demonstrates a ligand‐based strategy for controlling nanocluster structure and also provides a method for the discovery of possibly overlooked clusters because of their anomalous solubility.