Department of Chemistry, National Dong Hwa University, No. 1, Sec 2, Da Hsueh Rd., Hualien, 97401, Taiwan, R.O.C.
CNRS, ISCR-UMR 6226, Univ Rennes, 35000, Rennes, France.
Chemistry. 2023 Jun 2;29(31):e202300730. doi: 10.1002/chem.202300730. Epub 2023 Apr 17.
The first 8-electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg (dtp) ] (dtp=S P(O Pr) ) 1 and [PdHAg (dtp) ] 2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of trifluoroacetic acid, resulting in the formation of 2 in 55 % yield. Further modification of the shell results in the formation of [PdAg (dtp) ] 3 via an internal redox reaction, with the system retaining an 8-electron superatomic configuration. The interstitial hydride in 1 and 2 contributes its 1s electron to the superatomic electron count and occupies a PdAg tetrahedron. The distributions of isomers corresponding to different dispositions of the outer capping Ag atoms are investigated by multinuclear VT NMR spectroscopy. The emissive state of 3 has a lifetime of 200 μs (λ =448; λ =842), while 1 and 2 are non-emissive. The catalytic reduction of 4-nitrophenol is demonstrated with 1-3 at room temperature.
报道了首例具有间隙氢化物[PdHAg(dtp)]（dtp=S P(O Pr) ）1和[PdHAg(dtp)]2的 8 电子 Pd/Ag 超原子合金。通过与 1 当量的三氟乙酸反应，可实现将单个 Ag 原子靶向添加到 1 中，从而以 55%的收率生成 2。进一步修饰外壳会导致通过内部氧化还原反应形成[PdAg(dtp)]3，该体系保留 8 电子超原子构型。1 和 2 中的间隙氢化物将其 1s 电子贡献给超原子电子计数，并占据 PdAg 四面体。通过多核 VT NMR 光谱研究了不同位置的外部盖帽 Ag 原子的异构体分布。3 的发射态寿命为 200μs（λ=448；λ=842），而 1 和 2 则不发光。在室温下，用 1-3 进行了对 4-硝基苯酚的催化还原。
