Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei 230601, P. R. China.
Key Laboratory of Structure and Functional Regulation of Hybrid Materials, Ministry of Education, Anhui University, Hefei 230601, P. R. China.
Nanoscale Horiz. 2022 Oct 24;7(11):1397-1403. doi: 10.1039/d2nh00321j.
For metal nanoclusters with the "cluster of clusters" intramolecular evolution pattern, most efforts have been made towards the vertical superposition of icosahedral nanobuilding blocks (, from mono-icosahedral Au to bi-icosahedral Au and tri-icosahedral Au), while the horizontal expansion of these rod-shaped multi-icosahedral aggregates was largely neglected. We herein report the horizontal expansion of the biicosahedral M cluster framework, yielding an [AuAg(S-Adm)(DPPM)Cl] nanocluster that contains an AuAg kernel and six Au(DPPM)(S-Adm) peripheral wings. The structural determination of [AuAg(S-Adm)(DPPM)Cl] resolved a decades-long question towards rod-shaped multi-icosahedral aggregates: how to load bidentate phosphine and bulky thiol ligands onto the nanocluster framework? The structural comparison between [AuAg(S-Adm)(DPPM)Cl] and previously reported [AuAg(PPh)Cl] or [AuAg(SR)(PPh)Cl] rationalized the unique packing of Au(DPPM)(S-Adm) motif structures on the surface of the former nanocluster. Overall, this work presents the horizontal expansion of rod-shaped multi-icosahedral nanoclusters, which provides new insights into the preparation of novel icosahedron-based aggregates with both vertically and horizontally growing extensions.
对于具有“簇中簇”分子内进化模式的金属纳米簇，大多数研究都集中在二十面体纳米构建块的垂直叠加上（从单二十面体 Au 到双二十面体 Au 和三二十面体 Au），而这些棒状多二十面体聚集体的水平扩展在很大程度上被忽视了。我们在此报告了双二十面体 M 团簇框架的水平扩展，得到了一个包含 AuAg 核和六个 Au(DPPM)(S-Adm)外围翅膀的 [AuAg(S-Adm)(DPPM)Cl] 纳米簇。[AuAg(S-Adm)(DPPM)Cl] 的结构测定解决了一个长达数十年的关于棒状多二十面体聚集体的问题：如何将双齿膦和大体积硫醇配体负载到纳米簇框架上？[AuAg(S-Adm)(DPPM)Cl] 与之前报道的 [AuAg(PPh)Cl] 或 [AuAg(SR)(PPh)Cl] 的结构比较，解释了前者纳米簇表面上 Au(DPPM)(S-Adm) 结构基元独特的堆积方式。总的来说，这项工作展示了棒状多二十面体纳米簇的水平扩展，为制备具有垂直和水平生长扩展的新型基于二十面体的聚集体提供了新的思路。
