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Issue 3, 2017
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[Ag115S34(SCH2C6H4tBu)47(dpph)6]: synthesis, crystal structure and NMR investigations of a soluble silver chalcogenide nanocluster

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Abstract

With the aim to synthesize soluble cluster molecules, the silver salt of (4-(tert-butyl)phenyl)methanethiol [AgSCH2C6H4tBu] was applied as a suitable precursor for the formation of a nanoscale silver sulfide cluster. In the presence of 1,6-(diphenylphosphino)hexane (dpph), the 115 nuclear silver cluster [Ag115S34(SCH2C6H4tBu)47(dpph)6] was obtained. The molecular structure of this compound was elucidated by single crystal X-ray analysis and fully characterized by spectroscopic techniques. In contrast to most of the previously published cluster compounds with more than a hundred heavy atoms, this nanoscale inorganic molecule is soluble in organic solvents, which allowed a comprehensive investigation in solution by UV-Vis spectroscopy and one- and two-dimensional NMR spectroscopy including 31P/109Ag-HSQC and DOSY experiments. These are the first heteronuclear NMR investigations on coinage metal chalcogenides. They give some first insight into the behavior of nanoscale silver sulfide clusters in solution. Additionally, molecular weight determinations were performed by 2D analytical ultracentrifugation and HR-TEM investigations confirm the presence of size-homogeneous nanoparticles present in solution.

Graphical abstract: [Ag115S34(SCH2C6H4tBu)47(dpph)6]: synthesis, crystal structure and NMR investigations of a soluble silver chalcogenide nanocluster

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Publication details

The article was received on 13 Oct 2016, accepted on 06 Dec 2016 and first published on 15 Dec 2016


Article type: Edge Article
DOI: 10.1039/C6SC04578B
Citation: Chem. Sci., 2017,8, 2235-2240
  • Open access: Creative Commons BY license
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    [Ag115S34(SCH2C6H4tBu)47(dpph)6]: synthesis, crystal structure and NMR investigations of a soluble silver chalcogenide nanocluster

    S. Bestgen, O. Fuhr, B. Breitung, V. S. Kiran Chakravadhanula, G. Guthausen, F. Hennrich, W. Yu, M. M. Kappes, P. W. Roesky and D. Fenske, Chem. Sci., 2017, 8, 2235
    DOI: 10.1039/C6SC04578B

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