RESUMEN
Herein, we describe the synthesis of a toroidal Au10 cluster stabilized by N-heterocyclic carbene and halide ligands via reduction of the corresponding NHC-Au-X complexes (X = Cl, Br, I). The significant effect of the halide ligands on the formation, stability, and further conversions of these clusters is presented. While solutions of the chloride derivatives of Au10 show no change even upon heating, the bromide derivative readily undergoes conversion to form a biicosahedral Au25 cluster at room temperature. For the iodide derivative, the formation of a significant amount of Au25 was observed even upon the reduction of NHC-Au-I. The isolated bromide derivative of the Au25 cluster displays a relatively high (ca. 15%) photoluminescence quantum yield, attributed to the high rigidity of the cluster, which is enforced by multiple CH-π interactions within the molecular structure. Density functional theory computations are used to characterize the electronic structure and optical absorption of the Au10 cluster. 13C-Labeling is employed to assist with characterization of the products and to observe their conversions by NMR spectroscopy.
RESUMEN
The use of metal nanoclusters is strongly reliant on their size and configuration; hence, studying the potential isomers of a cluster is extremely beneficial in understanding their performance. In general, the prediction and identification of isomer structures and their properties can be challenging and computationally expensive. Our work describes an investigation to find local isomers for the previously experimentally characterized small gold cluster [Au6(NHC-S)4]2+ protected by bidentate mixed carbene-thiolate ligands. We employ the molecular dynamics simulation method where the interatomic forces are calculated from density functional theory. We find several isomers that are more stable than the isomer corresponding to the experimental crystal structure, as well as a significant impact of the finite-temperature atom dynamics on the electronic structure and optical properties. Our work highlights the growing need to investigate ligand-stabilized metal clusters to uncover isomerism and temperature effects on their properties.
