Compression‐Driven Internanocluster Reaction for Synthesis of Unconventional Gold Nanoclusters. (22nd April 2021)

• Record Type: Journal Article
• Authors: Gan, Zibao; Xia, Nan; Yan, Nan; Zhuang, Shengli; Dong, Jingwu; Zhao, Yan; Jiang, Shuqing; Tao, Qiang; Wu, Zhikun
• Is Part Of: Angewandte Chemie. Volume 133:Number 22(2021)
• Page Start: 12361
• Page End: 12365
• Publication Date: 2021-04-22
• Subjects: compression -- internanocluster reaction -- nanoclusters -- photoluminescence -- tri-interlocked staples; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202014828
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Can the active kernels in ultrasmall metal nanoparticles (nanoclusters, NCs) react with one another, or can the internanocluster reaction occur when they are in close enough proximity? To resolve this fundamental issue, we investigated the solid‐state internanocluster reaction of the most studied gold NC Au25 (SR)18 (SR: thiolate). A novel NC was produced by increasing the pressure to 5 GPa, whose composition was determined to be Au32 (SC2 H4 Ph)24 by mass spectrometry and thermogravimetric analysis. As revealed by single‐crystal X‐ray crystallography, the structure, a bicuboid Au14 kernel and three pairs of interlocked trimetric staples, has not been reported and endows the NC with obvious photoluminescence. DFT calculations indicate that the staples contribute substantially to the absorption properties. Further experiments reveal the pressure (internanocluster distance) can tune the internanocluster reaction, and the resulting product is not necessarily the thermodynamic product. Abstract : The compression‐driven internanocluster reaction in the solid state of Au25 was firstly demonstrated by introducing high pressure technology and a novel unconventional NC Au32 (SC2 H4 Ph)24 was obtained. Au32 (SC2 H4 Ph)24 NC consists of a bicuboid Au14 kernel and three pairs of interlocked trimetric staples, which has not been previously reported and endows it with enhanced photoluminescence.