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

• Published in: Angewandte Chemie International Edition 2016-06, Vol.55 (23), p.6694-6697
• Main Authors: Higaki, Tatsuya, Liu, Chong, Zeng, Chenjie, Jin, Renxi, Chen, Yuxiang, Rosi, Nathaniel L., Jin, Rongchao
• Format: Article
• Language: English
• Subjects: Alloys; Atomic structure; Benzene; Close packed lattices; Clusters; Face centered cubic lattice; Gold; Ligands; Nanoclusters; Nanostructure; nanostructures; Solubility; Solvents; Strategy; thiols
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201601947

We report the X‐ray structure of a gold nanocluster with 30 gold atoms protected by 18 1‐adamantanethiolate ligands (formulated as Au30(S‐Adm)18). This nanocluster exhibits a threefold rotationally symmetrical, hexagonal‐close‐packed (HCP) Au18 kernel protected by six dimeric Au2(SR)3 staple motifs. This new structure is distinctly different from the previously reported Au30S(S‐tBu)18 nanocluster protected by 18 tert‐butylthiolate ligands and one sulfido ligand with a face‐centered cubic (FCC) Au22 kernel. The Au30(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. In control: Structural control of an Au30 nanocluster is realized through a strategy based on the use of the 1‐adamantanethiol ligand to stabilize the metal core. The newly obtained Au30(S‐Adm)18 nanocluster comprises a hexagonal‐close‐packed kernel protected by six dimeric Au2(SR)3 motifs. This structure is different from a previously reported Au30S(S‐tBu)18 cluster that comprises a face‐centered‐cubic kernel.