Controlled Sequential Doping of Metal Nanocluster

Atomically precise doping of metal nanoclusters provides
excellent
opportunities not only for subtly tailoring their properties but also
for in-depth understanding of composition (structure)–property
correlation of metal nanoclusters and has attracted increasing interest
partly due to its significance for fundamental research and practical
applications. Although single and multiple metal atom doping of metal
nanoclusters (NCs) has been achieved, sequential single-to-multiple
metal atom doping is still a big challenge and has not yet been reported.
Herein, by introducing a second ligand, a novel multistep synthesis
method was developed, controlled sequential single-to-multiple metal
atom doping was successfully achieved for the first time, and three
doped NCs Au25Cd1(p-MBT)17(PPh3)2, Au18Cd2(p-MBT)14(PPh3)2, and [Au19Cd3(p-MBT)18]− (p-MBTH: para-methylbenzenethiol) were obtained, including two novel NCs that
were precisely characterized via mass spectrometry, single-crystal
X-ray crystallography, and so forth. Furthermore, sequential doping-induced
evolutions in the atomic and crystallographic structures and optical
and catalytic properties of NCs were revealed.

对金属纳米簇进行原子级精确掺杂不仅为巧妙调节其性质提供了卓越的机遇，而且有助于深入探究金属纳米簇的组成（结构）与性能之间的关联，从而吸引了日益增长的关注，部分原因在于其对基础研究和实际应用的重要性。尽管金属纳米簇（NCs）的单个和多个金属原子掺杂已取得进展，但逐级单到多金属原子掺杂仍然是一项重大挑战，尚未有相关报道。在本研究中，通过引入第二配体，开发了一种新颖的多步骤合成方法，首次实现了对金属纳米簇的受控逐级单到多金属原子掺杂，并成功合成了三种掺杂的纳米簇Au25Cd1(p-MBT)17(PPh3)2、Au18Cd2(p-MBT)14(PPh3)2和[Au19Cd3(p-MBT)18]−（p-MBTH：对甲基苯硫醇），其中包含两种新型纳米簇，它们通过质谱、单晶X射线晶体学等方法进行了精确表征。此外，还揭示了逐级掺杂导致的纳米簇的原子和晶体结构以及光学和催化性能的变化。