Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213 (USA).
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, 2699 Qianjin Street, Changchun, Jilin 130012 (P. R. China).
Angew Chem Int Ed Engl. 2015 Aug 17;54(34):9826-9. doi: 10.1002/anie.201502667. Epub 2015 Jul 1.
The structure of nanoparticles plays a critical role in dictating their material properties. Gold is well known to adopt face-centered cubic (fcc) structure. Herein we report the first observation of a body-centered cubic (bcc) gold nanocluster composed of 38 gold atoms protected by 20 adamantanethiolate ligands and two sulfido atoms ([Au38S2(SR)20], where R=C10H15) as revealed by single-crystal X-ray crystallography. This bcc structure is in striking contrast with the fcc structure of bulk gold and conventional Au nanoparticles, as well as the bi-icosahedral structure of [Au38(SCH2CH2Ph)24]. The bcc nanocluster has a distinct HOMO-LUMO gap of ca. 1.5 eV, much larger than the gap (0.9 eV) of the bi-icosahedral [Au38(SCH2CH2Ph)24]. The unique structure of the bcc gold nanocluster may be promising in catalytic applications.
纳米粒子的结构在决定其材料性质方面起着关键作用。金通常采用面心立方（fcc）结构。在此，我们首次观察到由 38 个金原子组成的体心立方（bcc）金纳米团簇，该团簇由 20 个金刚烷硫醇配体和两个硫原子保护([Au38S2(SR)20]，其中 R=C10H15)，这是通过单晶 X 射线晶体学揭示的。这种 bcc 结构与体相金和传统 Au 纳米粒子的 fcc 结构以及[Au38(SCH2CH2Ph)24]的双二十面体结构形成鲜明对比。bcc 纳米团簇具有明显的 HOMO-LUMO 能隙约为 1.5eV，远大于双二十面体[Au38(SCH2CH2Ph)24]的间隙（0.9eV）。bcc 金纳米团簇的独特结构在催化应用中可能具有广阔的前景。
