Superatom Pruning by Diphosphine Ligands as a Chemical Scissor

• Published in: Inorganic chemistry Vol. 62; no. 9; pp. 3866 - 3874
• Main Authors: Tseng, Yu-Ming, Liao, Jian-Hong, Chiu, Tzu-Hao, Liang, Hao, Kahlal, Samia, Saillard, Jean-Yves, Liu, C. W.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 06.03.2023
• Subjects: Chemical Sciences; Coordination chemistry; Cristallography
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.2c04157

A two-electron silver superatom, [Ag6{S2P­(O i Pr)2}4(dppm)2] (1), was synthesized by adding dppm (bis­(diphenyl­phosphino)­methane) into [Ag20{S2P­(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 Ag20 nanocluster (NC) to an octahedral Ag6 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.