Bestgen Sebastian, Fuhr Olaf, Breitung Ben, Kiran Chakravadhanula Venkata Sei, Guthausen Gisela, Hennrich Frank, Yu Wen, Kappes Manfred M, Roesky Peter W, Fenske Dieter
Institute of Inorganic Chemistry , Karlsruhe Institute of Technology (KIT) , Engesserstraße 15 , 76131 Karlsruhe , Germany . Email:
Institute of Nanotechnology and Karlsruhe Nano Micro Facility (KNMF) , Karlsruhe Institute of Technology (KIT) , Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen , 76021 Karlsruhe , Germany.
Chem Sci. 2017 Mar 1;8(3):2235-2240. doi: 10.1039/c6sc04578b. Epub 2016 Dec 15.
With the aim to synthesize soluble cluster molecules, the silver salt of (4-(-butyl)phenyl)methanethiol [AgSCHCH Bu] 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 [AgS(SCHCH Bu)(dpph)] 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 P/Ag-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.
为了合成可溶性簇分子，将（4-（-丁基）苯基）甲硫醇的银盐[AgSCHCH Bu]用作形成纳米级硫化银簇的合适前体。在1,6-（二苯基膦基）己烷（dpph）存在下，得到了115核银簇[AgS(SCHCH Bu)(dpph)]。通过单晶X射线分析阐明了该化合物的分子结构，并通过光谱技术进行了全面表征。与大多数先前发表的含有一百多个重原子的簇化合物不同，这种纳米级无机分子可溶于有机溶剂，这使得通过紫外-可见光谱以及包括P/Ag-HSQC和DOSY实验在内的一维和二维核磁共振光谱在溶液中进行全面研究成为可能。这些是对造币金属硫族化物的首次异核核磁共振研究。它们对纳米级硫化银簇在溶液中的行为提供了一些初步见解。此外，通过二维分析超速离心法进行了分子量测定，高分辨率透射电子显微镜研究证实了溶液中存在尺寸均一的纳米颗粒。
