Overall structure of Au12Ag60(S-c-C6H11)31Br9(Dppp)6: achieving a stronger assembly of icosahedral M13 units
Overall structure of Au12Ag60(S-c-C6H11)31Br9(Dppp)6: achieving a stronger assembly of icosahedral M13 units
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Au12Ag60(S-c-C6H11)31Br9(Dppp)6的整体结构：实现更强的二十面体M13单元组装
DOI：
10.1039/d2nr06613k
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发表时间：
2022-12-29
期刊：
影响因子：
6.7
通讯作者：
Zhu，Manzhou
中科院分区：
文献类型：
--
作者：
Zhou，Manman;Li，Kang;Zhu，Manzhou
精确的原子组装的纳米团簇提供了一个很好的平台来阐明积木组装的演变。本文报道了一种大的二十面体（M1, 3）基银-金合金纳米团簇[Au 12 Ag 60（S-c-C6 H 11）31 Br 9（Dppp）6] Br 2（dppp = 1，3-双（二苯基膦基）丙烷）。在结构上，Au 12 Ag 60由Au 12 Ag 40内核组成，其被视为十个扭曲的完整二十面体（M13）和两个缺失的二十面体（M12）的相互渗透，并且被复杂的金属有机壳包围。得益于额外掺杂的8至12个Au原子，八聚体组装增加到12聚体组装。采用含时密度泛函理论（TDDFT）和Tamm-Dancoff近似（TDA）方法研究了Au 12 Ag 60和Au 8 Ag 57的光学性质差异.结果表明，Au原子数量的不同导致了不同的光学性质。此外，瞬态吸收光谱（TA）也进行了，揭示了一个十二聚体组装大大提高了激发态寿命。[Au 12 Ag 60（S-c-C6 H11）31 Br 9（Dppp）6] Br 2合金纳米团簇在二十面体M13组装体的数量方面提供了突破，即，实现了12-mer组装，有助于阐明M13基组装纳米团簇的熔融生长及其几何/电子结构相关性，这将促进M13纳米结构单元组装的进一步研究，特别是其光学性质的研究.
Precise atomically assembled nanoclusters provide a great platform to elucidate the evolution of the assembly of building blocks. Herein, a large icosahedral (M13)-based silver–gold alloy nanocluster [Au12Ag60(S-c-C6H11)31Br9(Dppp)6]Br2 (dppp = 1,3-bis(diphenylphosphino)propane) is reported. Structurally, Au12Ag60 consists of an Au12Ag40 kernel, which is viewed as the interpenetration of ten twisted complete icosahedrons (M13) and two missing icosahedrons (M12), and this is surrounded by a complex metal–organic shell. Benefiting from the extra doping of eight to twelve Au atoms, the octameric assembly was increased to a twelve-mer assembly. The time-dependent density functional theory (TDDFT) method with a Tamm–Dancoff approximation (TDA) was performed to investigate the difference in the optical properties of Au12Ag60 and Au8Ag57. The results indicate that the difference in the amount of Au atoms results in different optical properties. Furthermore, transient absorption spectroscopy (TA) was also performed, revealing that a twelve-mer assembly greatly enhances the excited-state lifetime. The [Au12Ag60(S-c-C6H11)31Br9(Dppp)6]Br2 alloy nanocluster has provided a breakthrough in the number of icosahedral M13 assemblies, i.e., achieving a twelve-mer assembly, helping to elucidate the fusion growth of M13-based assembled nanoclusters as well as their geometric/electronic structure correlations, which will promote further research on the assembly of M13 nano-building blocks, especially on their optical properties.