Gold–Thiolate Ring as a Protecting Motif in the Au20(SR)16Nanocluster and Implications,Journal of the American Chemical Society

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Gold–Thiolate Ring as a Protecting Motif in the Au20(SR)16Nanocluster and Implications
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2014-08-15 , DOI: 10.1021/ja506802n
Chenjie Zeng ₁ , Chong Liu ₂ , Yuxiang Chen ₁ , Nathaniel L. Rosi ₂ , Rongchao Jin ₁

Affiliation

Understanding how gold nanoclusters nucleate from Au(I)SR complexes necessitates the structural elucidation of nanoclusters with decreasing size. Toward this effort, we herein report the crystal structure of an ultrasmall nanocluster formulated as Au20(TBBT)16 (TBBT = SPh-t-Bu). The structure features a vertex-sharing bitetrahedral Au7 kernel and an unprecedented "ring" motif-Au8(SR)8. This large ring protects the Au7 kernel through strong Auring-Aukernel bonding but does not involve S-Aukernel bonding, in contrast to the common "staple" motifs in which the S-Aukernel bonding is dominant but the Austaple-Aukernel interaction is weak (i.e., aurophilic). As the smallest member in the TBBT "magic series", Au20(TBBT)16, together with Au28(TBBT)20, Au36(TBBT)24, and Au44(TBBT)28, reveals remarkable size-growth patterns in both geometric structure and electronic nature. Moreover, Au20(TBBT)16, together with the Au24(SR)20 and Au18(SR)14 nanoclusters, forms a "4e" nanocluster family, which illustrates a trend of shrinkage of bitetrahedral kernels from Au8(4+) to Au7(3+) and possibly to Au6(2+) with decreasing size.

中文翻译：

金硫醇环作为 Au20(SR)16 纳米团簇中的保护基序及其意义

了解金纳米团簇如何从 Au(I)SR 复合物成核需要对尺寸减小的纳米团簇进行结构阐明。为了这一努力，我们在此报告了一个超小纳米团簇的晶体结构，该团簇被定义为 Au20(TBBT)16 (TBBT = SPh-t-Bu)。该结构具有顶点共享双四面体 Au7 内核和前所未有的“环”基序-Au8(SR)8。这个大环通过强 Auring-Aukernel 键合保护 Au7 核，但不涉及 S-Aukernel 键合，与常见的“主食”基序形成对比，其中 S-Aukernel 键合占主导，但 Austaple-Aukernel 相互作用较弱（即, 嗜热）。作为TBBT“魔法系列”中最小的成员Au20(TBBT)16，连同Au28(TBBT)20、Au36(TBBT)24、Au44(TBBT)28，揭示了几何结构和电子性质的显着尺寸增长模式。此外，Au20(TBBT)16 与 Au24(SR)20 和 Au18(SR)14 纳米团簇形成“4e”纳米团簇家族，这说明了双四面体核从 Au8(4+) 向 Au7( 3+) 和可能到 Au6(2+) 尺寸减小。

更新日期：2014-08-15

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