Li Jiao-Jiao, Liu Zhikun, Guan Zong-Jie, Han Xu-Shuang, Shi Wan-Qi, Wang Quan-Ming
Department of Chemistry, Key Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084, P. R. China.
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Liangxiang Campus, Beijing Institute of Technology, Beijing 102488, P. R. China.
J Am Chem Soc. 2022 Jan 19;144(2):690-694. doi: 10.1021/jacs.1c11643. Epub 2022 Jan 7.
An atomically resolved gold nanocluster Au(C≡CCH-2,4-F) () with an unusual 59 valence electrons has been synthesized. Single-crystal X-ray diffraction reveals that its Au kernel is a Au Marks decahedron capped by two Au units. The surface structure of consists of 20 linear Au(C≡CR) staples. Intercluster interactions are observed between these symmetric clusters. The existence of an unpaired electron is verified by magnetic measurement. Interestingly, this open-shell gold cluster stays intact in toluene solution at 80 °C for more than a week, and it has good charging-discharging capability under electrochemical conditions. The compact ligand shell protection around the symmetric core accounts for the high stability. This work suggests that geometric factors may play a crucial role in determining the stability of a metal nanocluster, even though the cluster has an open-shell electronic structure.
已合成出具有不寻常59个价电子的原子分辨金纳米团簇Au(C≡CCH-2,4-F)()。单晶X射线衍射表明其金核是由两个金单元封顶的金马克斯十面体。其表面结构由20个线性Au(C≡CR)钉组成。在这些对称簇之间观察到簇间相互作用。通过磁性测量验证了未成对电子的存在。有趣的是，这种开壳层金簇在80℃的甲苯溶液中能保持完整超过一周，并且在电化学条件下具有良好的充放电能力。对称核周围紧凑的配体壳层保护解释了其高稳定性。这项工作表明，即使该簇具有开壳层电子结构，几何因素在决定金属纳米团簇的稳定性方面可能也起着关键作用。
