Dithiophosphonate-Protected Eight-Electron Superatomic Ag Nanocluster: Synthesis, Isomerism, Luminescence, and Catalytic Activity.

The structure-property relationship considering isomerism-tuned photoluminescence and efficient catalytic activity of silver nanoclusters (NCs) is exclusive. Asymmetrical dithiophosphonate NH[SP(OR)(-CHOCH)] ligated first atomically precise silver NCs [Ag{SP(OR)(-CHOCH)}]PF {where, R = Pr (), Et ()} were established by single-crystal X-ray diffraction and characterized by electrospray ionization mass spectrometry, NMR (P, H, H), X-ray photoelectron spectroscopy, UV-visible, energy-dispersive X-ray spectroscopy, Fourier transforms infrared, thermogravimetric analysis, etc. NCs and consist of eight silver atoms in a cubic framework and enclose an Ag@Ag-centered icosahedron to constitute an Ag core of symmetry, which is concentrically inscribed within the S snub-cube, P cuboctahedron, and the O truncated tetrahedron formed by 12 dithiophosphonate ligands. These NCs facilitate to be an eight-electron superatom (1S1P), in which eight capping Ag atoms exhibit structural isomerism with documented isoelectronic [Ag{SP(OPr)}]PF . In contrast to , the stapling of dithiophosphonates in and triggered bluish emission within the 400 to 500 nm region at room temperature. The density functional theory study rationalized isomerization and optical properties of , , and . Both (, and ) clusters catalyzed a decarboxylative acylarylation reaction for rapid oxindole synthesis in 99% yield under ambient conditions and proposed a multistep reaction pathway. Ultimately, this study links nanostructures to their physical and catalytic properties.