Han Jiaojiao, Li Hao, Shen Honglei, Xu Ying, Zou Xuejuan, Kang Xi, Zhu Manzhou
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei, Anhui 230601, China.
Precis Chem. 2023 Mar 16;1(3):139-145. doi: 10.1021/prechem.2c00007. eCollection 2023 May 22.
Monolayer-protected nanoclusters are ideal models for understanding the correlations between structures and properties of inorganic nanoparticles, especially for those molecules with identical sizes but comparable structures. Here, we controllably prepared and structurally determined a valence-neutral Au Ag (SPh Bu) (0 < < 4) nanocluster with comparable structure features to a well-known AuAg(SPhF) cluster. The Au Ag (SPh Bu) cluster contained a hollow Au@M metallic kernel (M = Au/Ag), 12 Au(SR) staples, and two bridging SR molecules, and its average molecular formula was determined to be AuAg(SPh Bu), as evidenced by X-ray crystallography and electrospray ionization mass spectrometry. Because of the ligand effect and the asymmetrical arrangement of the Au dopants in the dodecahedral cage, the Au Ag (SPh Bu) nanocluster exhibited lower molecular symmetry relative to AuAg(SPhF) in terms of the dodecahedral kernel and motif shell structures. Besides, the strong π-π interaction in Au Ag (SPh Bu) contributed to its enhanced photoluminescence intensity compared with AuAg(SPhF). The study, herein, extends the 44-metal-atom cluster family, thereby enabling us to better understand the correlations between their structures and properties at the atomic level.
单层保护的纳米团簇是理解无机纳米颗粒结构与性质之间相关性的理想模型，尤其适用于那些尺寸相同但结构可比的分子。在此，我们可控地制备并确定了一种价态中性的AuₓAg₄₋ₓ(SPhⁿBu)₄（0 < x < 4）纳米团簇的结构，其结构特征与著名的AuAg(SPhF)₄团簇相似。AuₓAg₄₋ₓ(SPhⁿBu)₄团簇包含一个中空的Au@M金属核（M = Au/Ag）、12个Au(SR)钉状物和两个桥连的SR分子，通过X射线晶体学和电喷雾电离质谱法确定其平均分子式为AuAg(SPhⁿBu)₄。由于配体效应以及十二面体笼中Au掺杂剂的不对称排列，就十二面体核和 motif 壳结构而言，AuₓAg₄₋ₓ(SPhⁿBu)₄纳米团簇相对于AuAg(SPhF)₄表现出较低的分子对称性。此外，AuₓAg₄₋ₓ(SPhⁿBu)₄中强烈的π-π相互作用导致其光致发光强度相对于AuAg(SPhF)₄有所增强。本文的研究扩展了44金属原子团簇家族，从而使我们能够在原子水平上更好地理解它们的结构与性质之间的相关性。
