Department of Chemistry, Key Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing, 100084, P. R. China.
Department of Applied Physics, Aalto University, Otakaari 1, 02150, Espoo, Finland.
Angew Chem Int Ed Engl. 2021 May 10;60(20):11430-11435. doi: 10.1002/anie.202100972. Epub 2021 Apr 7.
Silver nanoclusters containing Ag atoms protected by amino acids were synthesized and characterized. Chiral superatomic silver nanoclusters [Ag L (C≡C Bu) ]BF (L=l-/d-valine or l-/d-isoleucine) have been prepared by reducing AgC≡C Bu and amino acids (AAs) with NaBH . Single crystal X-ray diffraction revealed that these clusters have T symmetry, and the Ag metal kernel can be viewed as a tetracapped truncated tetrahedron (Ag ) surrounded with six W-shaped Ag units. The clusters are homochiral as evidenced by CD measurements. As for the strong CD signals, large contributions are found from the occupied Ag s,p states (superatomic D states) near the Fermi level. Electron counting revealed that these clusters are 18-electron systems, suggesting they are superatomic clusters. The superatomic nature with a 1S 1P 1D configuration was supported by DFT calculations. This work paves the way of taking AAs as facile chiral induction agents for the synthesis of metal nanoclusters.
合成并表征了由氨基酸保护的含 Ag 原子的银纳米簇。通过还原 AgC≡C Bu 和氨基酸（AA）与 NaBH ，制备了手性超原子银纳米簇[Ag L（C≡C Bu）]BF（L=l-/d-缬氨酸或 l-/d-异亮氨酸）。单晶 X 射线衍射表明这些簇具有 T 对称性，Ag 金属核可视为被六个 W 形 Ag 单元包围的四帽截角四面体（Ag ）。CD 测量表明这些簇是手性的。对于强 CD 信号，发现在费米能级附近的占据的 Ag s，p 态（超原子 D 态）有很大的贡献。电子计数表明这些簇是 18 电子体系，表明它们是超原子簇。DFT 计算支持具有 1S 1P 1D 构型的超原子性质。这项工作为使用 AA 作为金属纳米簇合成的简便手性诱导剂铺平了道路。
