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Article Dans Une Revue Inorganic Chemistry Année : 2023

Superatom Pruning by Diphosphine Ligands as a Chemical Scissor

Jian-Hong Liao
Hao Liang
Samia Kahlal
C W Liu

Résumé

A two-electron silver superatom, [Ag(6){S(2)P(O(i)Pr)(2)}(4)(dppm)(2)] (1), was synthesized by adding dppm (bis(diphenylphosphino)methane) into [Ag(20){S(2)P(O(i)Pr)(2)}(12)] (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(20) nanocluster (NC) to an octahedral Ag(6) 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 1 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.
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Dates et versions

hal-04013811 , version 1 (11-05-2023)

Identifiants

Citer

Yu-Ming Tseng, Jian-Hong Liao, Tzu-Hao Chiu, Hao Liang, Samia Kahlal, et al.. Superatom Pruning by Diphosphine Ligands as a Chemical Scissor. Inorganic Chemistry, 2023, 62 (9), pp.3866-3874. ⟨10.1021/acs.inorgchem.2c04157⟩. ⟨hal-04013811⟩
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