Total Structure and Electronic Structure Analysis of Doped Thiolated Silver [MAg24(SR)18](2-) (M = Pd, Pt) Clusters

Juanzhu Yan; Haifeng Su; Huayan Yang; Sami Malola; Shuichao Lin; Hannu Häkkinen; Nanfeng Zheng

doi:10.1021/jacs.5b07186

Total Structure and Electronic Structure Analysis of Doped Thiolated Silver [MAg24(SR)18](2-) (M = Pd, Pt) Clusters

J Am Chem Soc. 2015 Sep 23;137(37):11880-3. doi: 10.1021/jacs.5b07186. Epub 2015 Sep 14.

Authors

Juanzhu Yan¹, Haifeng Su¹, Huayan Yang¹, Sami Malola², Shuichao Lin¹, Hannu Häkkinen², Nanfeng Zheng¹

Affiliations

¹ State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
² Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä , FI-40014 Jyväskylä, Finland.

PMID: 26351859
DOI: 10.1021/jacs.5b07186

Abstract

With the incorporation of Pd or Pt atoms, thiolated Ag-rich 25-metal-atom nanoclusters were successfully prepared and structurally characterized for the first time. With a composition of [PdAg24(SR)18](2-) or [PtAg24(SR)18](2-), the obtained 25-metal-atom nanoclusters have a metal framework structure similar to that of widely investigated Au25(SR)18. In both clusters, a M@Ag12 (M = Pd, Pt) core is capped by six distorted dimeric -RS-Ag-SR-Ag-SR- units. However, the silver-thiolate overlayer gives rise to a geometric chirality at variance to Au25(SR)18. The effect of doping on the electronic structure was studied through measured optical absorption spectra and ab initio analysis. This work demonstrates that modulating electronic structures by transition-metal doping is expected to provide effective means to manipulate electronic, optical, chemical, and catalytic properties of thiolated noble metal nanoclusters.