Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China.
Key Laboratory of Ion Beam Bioengineering, Institute of Technical Biology and Agriculture Engineering, Chinese Academy of Sciences, Hefei 230031, China.
Nat Commun. 2017 Mar 24;8:14739. doi: 10.1038/ncomms14739.
Metal nanoclusters have recently attracted extensive interest not only for fundamental scientific research, but also for practical applications. For fundamental scientific research, it is of major importance to explore the internal structure and crystallographic arrangement. Herein, we synthesize a gold nanocluster whose composition is determined to be AuS(SCHPh) by using electrospray ionization mass spectrometry and single crystal X-ray crystallography (SCXC). SCXC also reveals that AuS(SCHPh) consists of a fcc-like Au kernel protected by a pair of giant AuS(SCHPh) staple motifs, which contain 6 tetrahedral-coordinate μ-S atoms not previously reported in the Au-S interface. Importantly, the fourth crystallographic closest-packed pattern, termed 6H left-handed helical (6HLH) arrangement, which results in the distinct loss of solid photoluminescence of amorphous AuS(SCHPh), is found in the crystals of AuS(SCHPh). The solvent-polarity-dependent solution photoluminescence is also demonstrated. Overall, this work provides important insights about the structure, Au-S bonding and solid photoluminescence of gold nanoclusters.
金属纳米团簇最近不仅在基础科学研究中引起了广泛的关注，而且在实际应用中也引起了广泛的关注。对于基础科学研究，探索其内部结构和晶体排列至关重要。在此，我们通过电喷雾电离质谱和单晶 X 射线晶体学（SCXC）合成了一种组成确定为 AuS(SCHPh)的金纳米团簇。SCXC 还揭示 AuS(SCHPh) 由一个 fcc 样的 Au 核保护，该核由一对巨大的 AuS(SCHPh)钉扎基序保护，其中包含 6 个以前在 Au-S 界面中未报道的四面体配位 μ-S 原子。重要的是，在 AuS(SCHPh) 的晶体中发现了第四种晶体最近邻堆积模式，称为 6H 左手螺旋（6HLH）排列，这导致非晶态 AuS(SCHPh)的固体光致发光明显丧失。还证明了溶剂极性依赖性溶液光致发光。总的来说，这项工作提供了关于金纳米团簇的结构、Au-S 键合和固体光致发光的重要见解。
