A Silver Nanocluster Containing Interstitial Sulfur and Unprecedented Chemical Bonds

Xu Liu; Jishi Chen; Jinyun Yuan; Yizhi Li; Jin Li; Shiming Zhou; Chuanhao Yao; Lingwen Liao; Shengli Zhuang; Yan Zhao; Haiteng Deng; Jinlong Yang; Zhikun Wu

doi:10.1002/anie.201805594

A Silver Nanocluster Containing Interstitial Sulfur and Unprecedented Chemical Bonds

Angew Chem Int Ed Engl. 2018 Aug 27;57(35):11273-11277. doi: 10.1002/anie.201805594. Epub 2018 Aug 1.

Authors

Xu Liu^{1

2

3}, Jishi Chen¹, Jinyun Yuan⁴, Yizhi Li⁵, Jin Li⁶, Shiming Zhou⁴, Chuanhao Yao¹, Lingwen Liao¹, Shengli Zhuang^{1

2

3}, Yan Zhao^{1

2

3}, Haiteng Deng⁶, Jinlong Yang⁴, Zhikun Wu^{1

3}

Affiliations

¹ 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, Anhui, 230031, China.
² Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, 230026, China.
³ Institute of Physical Science and Information Technology, Anhui University, Hefei, 230601, China.
⁴ Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, China.
⁵ State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
⁶ Tsinghua University-Peking University Joint center for Life Sciences, School of Life Sciences, Tsinghua University, Beijing, 100084, China.

PMID: 30010231
DOI: 10.1002/anie.201805594

Abstract

The emergence of thiolated metal nanoclusters provides opportunities to identify significant and unprecedented phenomena because they are at quantum sizes and can be characterized with X-ray crystallography. Recently silver nanoclusters have received extensive interest owing to their merits, such as low-cost and rich properties. Herein, a thiolated silver nanocluster [Ag₄₆ S₇ (SPhMe₂ )₂₄ ]NO₃ (Ag₄₆ for short) with a face-centered cubic (fcc) structure was successfully synthesized and structurally resolved by X-ray analysis. Most importantly, interstitial sulfur was found in the lattice void of Ag₄₆ without lattice distortion or expansion, indicating that the classic theory of interstitial metal solid solutions might be not applicable at quantum size. Furthermore, unprecedented chemical bonds and unique structural features (such as asymmetrically coordinated μ₄ -S) were found in Ag₄₆ and might be related to the interstitial sulfur, which is supported by natural population analyses.

Keywords: interstitial sulfur; nanoclusters; photoluminescence; silver; structure.