山东大学Zhi Wang小组通过层压不同阴离子模板实现了从Ag57到Ag72银簇的外延生长。2024年10月31日出版的《德国应用化学》发表了这项成果。

据介绍，阴离子模板在精确控制金属团簇的尺寸、几何形状和功能方面的能力是公认的。然而，由于巨大的合成挑战，开发一种系统的方法来编排银团簇的组装，特别是那些包含多种不同类型阴离子模板的团簇，仍然很困难。

在这项工作中，该团队报道了两种新的银材料，Ag57和Ag72，分别使用两种和三种不同的阴离子模板。Ag57具有陀螺仪状的一价阳离子，其Ag3三角形核被一个[SiW₉O₃₄]^10-还有三重Cl^-阴离子模板。

通过有意引入第三个阴离子模板SO₄^2-，该结构扩展到前所未有的Ag72（在Ag57的顶部外延生长了15个银原子），类似于一个玻璃杯，其中两个Ag3层由一个[SiW₉O₃₄]^10-，7个Cl^-还有一个SO₄^2-阴离子模板相对于纵向方向平行。

值得注意的是，Ag72表现出显著的结构复杂性，作为第一个包含三种不同类型阴离子模板的银晶体，它代表了一项开创性的成就。此外，Ag72比Ag57具有显著的优势，特别是在发光温度计和远程激光点火等应用方面。

附：英文原文

Title: Epitaxial Growth of Silver Clusters from Ag57 to Ag72 via Laminating Multiple Different Anion Templates

Author: Kai Sheng, Bao-Liang Han, Zhi Wang, Zhi-Yong Gao, Chen-Ho Tung, Di Sun

Issue&Volume: 2024-10-31

Abstract: The established capability of anion templates in precisely manipulating the size, geometry, and function of metal clusters is well acknowledged. However, the development of a systematic methodology for orchestrating the assembly of silver clusters, particularly those encompassing multiple distinct types of anion templates, remains elusive due to the formidable synthetic challenge. In this work, we report two novel silver clusters, Ag57 and Ag72, using two and three different anion templates, respectively. Ag57 features a gyroscope-like monovalent cation with an Ag3 triangle core sandwiched by one [SiW9O34]10 and a triad of Cl anion templates. By intentionally introducing the third anion template, SO42, the structure is expanded to the unprecedented Ag72 (with 15 silver atoms epitaxially grown on top of Ag57) resembling a tumbler, inside of which two Ag3 layers are laminated by one [SiW9O34]10, seven Cl and one SO42 anion templates in parallel with respect to longitudinal orientation. It is noteworthy that Ag72 exhibits remarkable structural complexity and represents a pioneering achievement as the first silver cluster incorporating three distinct types of anion templates. In addition, Ag72 demonstrates a significant advantage over Ag57, particular in terms of applications such as luminescent thermometers and remote laser ignition.

DOI: 10.1002/anie.202416065

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202416065