期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 61, 期 11, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202116965
关键词
-
资金
- National Natural Science Foundation of China [91961201, 21631007, 21971136, 22001145]
- Shuimu Tsinghua Scholar Program
- China Postdoctoral Science Foundation [2020T130343]
We report the structures, stability, and catalytic properties of two Ag-21 nanoclusters with different electronic structures and an identical icosahedral kernel. These clusters exhibit superior stability under ambient conditions and one of them shows higher activity as a catalyst in a reduction reaction.
We report the structures, stability and catalysis properties of two Ag-21 nanoclusters, namely [Ag-2(1)-(H(2)BTCA)(3)(O2PPh2)(6)]SbF6 (1) and [Ag-21(C (math)CC6H3-3,5-R-2)(6)(O2PPh2)(10)]SbF6 (2) (H(4)BECA=p-tert-butylthiacalix-[4]arene, R= OMe). Both Ag-21 structures possess an identical icosahedral kernel that is surrounded by eight peripheral Ag atoms. Single-crystal structural analysis and ESI-MS revealed that 1 is an 8-electron cluster and 2 has four free electrons. Theoretical results show that the P-symmetry orbitals are found as HOMO-1 and HOMO states in 1, and the frontier unoccupied molecular orbitals (LUMO, LUMO +1 and LUMO +2) show D-character, indicating 1 is a superatomic cluster with an electronically closed shell 1S(2)1P(2), while 2 has an incomplete shell configuration 1S(2)1P(2). These two Ag-21 clusters show superior stability under ambient conditions, and 1 is robust even at 90 degrees C in toluene and under oxidative conditions (30% H2O2). Significantly, 2 exhibits much higher activity than 1 as catalyst in the reduction of 4-nitrophenol. This work demonstrates that ligands can influence the electronic structures of silver clusters, and further affect their stability and catalytic performance.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据