Department of Chemistry, National Dong Hwa University, Hualien, Taiwan 97401, Republic of China.
Univ Rennes, CNRS, ISCR-UMR 6226, F-35000 Rennes, France.
Inorg Chem. 2023 Mar 6;62(9):3866-3874. doi: 10.1021/acs.inorgchem.2c04157. Epub 2023 Feb 21.
A two-electron silver superatom, [Ag{SP(OPr)}(dppm)] (), was synthesized by adding dppm (bis(diphenylphosphino)methane) into [Ag{SP(OPr)}] (8e). It was characterized by single-crystal crystallography, multinuclear NMR spectroscopy, electrospray ionization-mass spectrometry, density functional theory (DFT), and time-dependent DFT calculations. The added dppm ligands, which carry out the nanocluster-to-nanocluster transformation, act as a chemical scissor to prune the nanocluster geometrically from an icosahedron-based Ag nanocluster (NC) to an octahedral Ag NC and electronically from eight-electron to two-electron. Eventually, dppm was involved in the protective shell to form a new heteroleptic NC. The temperature-dependent NMR spectroscopy confirms its fluxional behavior, showing the fast atomic movement at ambient temperature. Compound exhibits a bright yellow emission under UV irradiation at ambient temperature with a quantum yield of 16.3%. This work demonstrates a new methodology to achieve nanocluster-to-nanocluster transformation via stepwise synthesis.
通过向 [Ag{SP(OPr)}]（8e）中添加 dppm（双（二苯基膦基）甲烷），合成了一个二电子银超原子 [Ag{SP(OPr)}(dppm)]（）。通过单晶 X 射线衍射、多核 NMR 光谱、电喷雾电离质谱、密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）计算对其进行了表征。添加的 dppm 配体作为化学剪刀，将纳米簇从基于二十面体的 Ag 纳米簇（NC）到八面体 Ag NC 进行几何形状修剪，并将电子从八电子修剪到二电子，从而实现了纳米簇到纳米簇的转变。最终，dppm 参与到保护壳中，形成了一个新的杂配 NC。温度依赖的 NMR 光谱证实了其通量行为，在环境温度下显示出快速的原子运动。在环境温度下，化合物在紫外光照射下发出亮黄色发射，量子产率为 16.3%。这项工作展示了一种通过逐步合成实现纳米簇到纳米簇转变的新方法。
