Shen Honglei, Wei Xiao, Xu Chao, Jin Shan, Wang Shuxin, Kang Xi, Zhu Manzhou
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei 230601, P. R. China.
College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, P. R. China.
Nanoscale. 2021 Apr 30;13(16):7694-7699. doi: 10.1039/d1nr00721a.
The structural determination of metastable nanoclusters remains challenging, which impedes the in-depth understanding of their structural evolution. Herein, based on a case study of Pd1Au9, we present a "cocrystallization-driven stabilization" approach to stabilize the metastable nanocluster and then determine its atomically precise structure. The [Pd1Au9(TFPP)7Br2]+ nanocluster is unstable in solution and would spontaneously convert to Pd2Au23(TFPP)10Br7. The introduction of Au11(TFPP)7Br3 nanocluster to the crystallization process of [Pd1Au9(TFPP)7Br2]+ gives rise to the cocrystallized Pd1Au9(TFPP)6Br3@Au11(TFPP)7Br3, although the composition of Pd1Au9 changes from [Pd1Au9(TFPP)7Br2]+ to Pd1Au9(TFPP)6Br3 among this cocrystallization. With this approach, the overall structure of the metastable Pd1Au9 has been determined. Owing to the very similar cluster size and surface ligand environment between Au11 and Pd1Au9, the obtained Pd1Au9@Au11 cocrystal exhibits almost the same cell parameters as those of the single crystalized Au11. Overall, the proposed "cocrystallization-driven stabilization" approach hopefully sheds light on the structural determination of more metastable nanoclusters.
亚稳态纳米团簇的结构测定仍然具有挑战性，这阻碍了对其结构演变的深入理解。在此，基于对Pd1Au9的案例研究，我们提出了一种“共结晶驱动稳定化”方法来稳定亚稳态纳米团簇，然后确定其原子精确结构。[Pd1Au9(TFPP)7Br2]+纳米团簇在溶液中不稳定，会自发转化为Pd2Au23(TFPP)10Br7。将Au11(TFPP)7Br3纳米团簇引入[Pd1Au9(TFPP)7Br2]+的结晶过程中，会产生共结晶的Pd1Au9(TFPP)6Br3@Au11(TFPP)7Br3，尽管在这种共结晶过程中，Pd1Au9的组成从[Pd1Au9(TFPP)7Br2]+变为Pd1Au9(TFPP)6Br3。通过这种方法，已确定了亚稳态Pd1Au9的整体结构。由于Au11和Pd1Au9之间的团簇尺寸和表面配体环境非常相似，所获得的Pd1Au9@Au11共晶体的晶胞参数与单晶化的Au11几乎相同。总体而言，所提出的“共结晶驱动稳定化”方法有望为更多亚稳态纳米团簇的结构测定提供启示。
