Synthesis, structural characterization and transformation of an eight-electron superatomic alloy, [Au@Ag19{S2P(OPr)2}12]. Issue 15 (4th April 2018)

• Record Type: Journal Article
• Authors: Lin, Yan-Ru; Kishore, Pilli V. V. N.; Liao, Jian-Hong; Kahlal, Samia; Liu, Yu-Chiao; Chiang, Ming-Hsi; Saillard, Jean-Yves; Liu, C. W.
• Is Part Of: Nanoscale. Volume 10:Issue 15(2018)
• Page Start: 6855
• Page End: 6860
• Publication Date: 2018-04-04
• Subjects: Nanoscience -- Periodicals; Nanotechnology -- Periodicals; 620.505
• DOI: 10.1039/c8nr00172c
• Languages: English
• ISSNs: 2040-3364

Abstract

Abstract : A superatomic alloy nanocluster (NC) [Au@Ag19 (dtp)12 ] from [Ag20 (dtp)12 ] has been synthesized and structurally characterized and its surface reconstruction to Au@Ag20 has been demonstrated. Abstract : Controlling the metal nanoclusters with atomic precision is highly difficult and further studies on their transformation reactions are even more challenging. Herein we report the controlled formation of a silver alloy nanocluster [AuAg19 {S2 P(O n Pr)2 }12 ] (1 ) from an Ag20 template via a galvanic exchange route. X-ray structural analysis reveals that the alloy structure comprises of a gold-centered Ag12 icosahedron, Au@Ag12, capped by seven silver atoms. Interestingly upon reacting with one equiv. of silver(i ) salt, (1 ) can transform into a higher nuclearity nanocluster, [Au@Ag20 {S2 P(O n Pr)2 }12 ] + (2 ). The conversion process is studied via ESI mass spectrometry and 31 P NMR spectroscopy. This kind of size-structural transformation at the single atom level is quite remarkable. Furthermore, the compositions of all the doped nanoclusters (1, 2 ) were fully characterized with ESI-MS and EDS. The blue shift depicted in the UV-visible and emission spectra of the doped nanoclusters (1, 2 ) compared with the precursor, Ag20, demonstrates that the doping atoms have significant effects on the electronic structures.