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Published on: May 9, 2014
Thiol-Induced Synthesis of Phosphine-Protected Gold Nanoclusters with Atomic Precision and Controlling the Structure
Shan Jin1, Wenjun Du1, Shuxin Wang1
1Department of Chemistry and Center for Atomic Engineering of Advanced Materials, AnHui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University , Hefei, Anhui 230601, People's Republic of China.
Abstract:
Efficient synthesis of atomically precise phosphine-capped gold nanocluster (with >10 metal atoms) is important to deeply understand the relationship between structure and properties. Herein, we successfully utilize the thiol-induced synthesis method and obtain three atomically precise phosphine-protected gold nanoclusters. Single-crystal X-ray structural analysis reveals that the nanoclusters are formulated as [Au13(Dppm)6](BPh4)3, [Au18(Dppm)6Br4](BPh4)2, and [Au20(Dppm)6(CN)6] (where Dppm stands for bis(diphenylphosphino)methane), which are further confirmed by electrospray ionization mass spectrometry, thermogravimetric analysis, and X-ray photoelectron spectroscopy. Meanwhile, [Au18(Dppm)6Br4](BPh4)2 could be converted into [Au13(Dppm)6](BPh4)3 and [Au20(Dppm)6(CN)6] by engineering the surface ligands under excess PPh3 or moderate NaBH3CN, respectively. Furthermore, according to the different binding ability of silver with halogen, we successfully achieved target metal exchange on [Au18(Dppm)6Br4](BPh4)2 with Ag-SAdm (where HS-Adm stands for 1-adamantane mercaptan) complex and obtained [AgxAu18-x(Dppm)6Br4](BPh4)2 (x = 1, 2) alloy nanoclusters. Our work will contribute to more intensive understanding on synthesizing phosphine-protected nanoclusters as well as shedding light on the structure-property correlations in the nanocluster range.
