An Atomically Precise Alkynyl-Protected PtAg42 Superatom Nanocluster and Its Structural Implications

作者：Shen Hui; Mizuta Tsutomu

来源：Chemistry-An Asian Journal, 2017, 12(22): 2904-2907.

DOI：10.1002/asia.201701337

<jats:title>Abstract</jats:title><jats:p>The synthesis and structure determination of an alkynyl‐protected Pt‐doped Ag superatom nanocluster, [PtAg<jats:sub>42</jats:sub>(C≡CC<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>CH<jats:sub>3</jats:sub>)<jats:sub>28</jats:sub>](SbF<jats:sub>6</jats:sub>)<jats:sub>6</jats:sub> <jats:bold>(1)</jats:bold>, are reported. The metallic core of this cluster can be viewed as a concentric three‐shell Russian doll comprising Pt@Ag<jats:sub>12</jats:sub>@Ag<jats:sub>30</jats:sub>, in which the missing icosidodecahedral Ag<jats:sub>30</jats:sub> shell and a new structural unit, M<jats:sub>43</jats:sub>, have been observed. On the surface of <jats:bold>1</jats:bold>, 28 alkynyl groups and 4 SbF<jats:sub>6</jats:sub><jats:sup>−</jats:sup> anions were found co‐protecting it. The protective role of SbF<jats:sub>6</jats:sub><jats:sup>−</jats:sup> in nanoclusters is unprecedented. Moreover, of the 28 alkynyl ligands, 12 are connected not only with the outermost Ag<jats:sub>30</jats:sub> shell, but also the inner Ag<jats:sub>12</jats:sub> shell through the twelve pentagonal faces of the outermost icosidodecahedral Ag<jats:sub>30</jats:sub> shell. Overall, by determining the crystal structure of <jats:bold>1</jats:bold>, we discovered the missing icosidodecahedral Ag<jats:sub>30</jats:sub> shell and the protective effect of SbF<jats:sub>6</jats:sub><jats:sup>−</jats:sup> anions and demonstrated a novel M<jats:sub>43</jats:sub> structural unit and the unique penetrability of pentagonal faces.</jats:p>

• 出版日期2017-11-16