Hu Feng, Yang Gaoyuan, Long Zhen-Chao, Shi Wan-Qi, Liang Gui-Jie, Wang Jia-Qi, Wang Quan-Ming
Department of Chemistry, Engineering Research Center of Advanced Rare Earth Materials (Ministry of Education), Tsinghua University, Beijing, 100084, P. R. China.
Hubei Key Laboratory of Low Dimensional Optoelectronic Materials and Devices, Hubei University of Arts and Science, Xiangyang, Hubei, 441053, P. R. China.
Small. 2025 May;21(21):e2502106. doi: 10.1002/smll.202502106. Epub 2025 Apr 1.
Isomerization of nanoclusters is helpful for understanding the relationships between structures and properties. Surface-protecting ligands play a crucial role in controlling the atomic packing mode of the inner core. The synthesis and total structural determination of the all alkynyl-protected gold nanocluster (NEtCHCl)[Au(C≡CCHPh)] (Au-1) are reported. Au-1 and the previously reported [Au(C≡CCH-4-CF)] (Au-2) constitute the largest alkynyl-protected nanocluster quasi-isomers (> 100 metal atoms). Both Au consist of an fcc Au kernel and a shell of 24 RC≡C─Au─C≡CR staples, but the specific arrangements are different. The application of the flexible alkynyl ligands creates a significant difference in the face-centered cubic (fcc) kernel structure in Au-1, showing a different electronic structure, thermal- and photo-stability. Transient absorption spectra reveal that Au-1 still does not show any metallic characteristics, even though it has a smaller energy gap (Eg) than Au-2.
纳米团簇的异构化有助于理解结构与性质之间的关系。表面保护配体在控制内核的原子堆积模式方面起着关键作用。本文报道了全炔基保护的金纳米团簇(NEtCHCl)[Au(C≡CCHPh)] (Au-1)的合成及完整结构测定。Au-1与先前报道的[Au(C≡CCH-4-CF)] (Au-2)构成了最大的炔基保护纳米团簇准异构体(>100个金属原子)。两者均由一个面心立方金内核和一个由24个RC≡C─Au─C≡CR钉状物组成的壳层构成，但具体排列方式不同。柔性炔基配体的应用使得Au-1的面心立方(fcc)内核结构产生了显著差异，表现出不同的电子结构、热稳定性和光稳定性。瞬态吸收光谱表明，尽管Au-1的能隙(Eg)比Au-2小，但它仍然没有表现出任何金属特性。
