In contrast to the corresponding inert bulk material, nanoscale gold clusters bear remarkable optical and catalytic properties that are highly dependent on the cluster size. Metal–organic frameworks (MOFs) have recently been identified as attractive host matrices for metallic clusters due to their confining porous environment. Through the rational choice of sulfonated ligands, we report the first encapsulation of a phosphine-stabilised Au₈ cluster into ZIF-8 via a bottle-around-ship approach. The cluster integrity within the MOF was proven by thorough characterisation including diffuse reflectance UV-visible spectroscopy and high-resolution transmission electron microscopy with elemental mapping. This strategy enabled precise control of cluster loadings from low (1.1 wt% Au) to high (8.2 wt% Au) values. The stabilising effect provided by the MOF was further analysed in temperature-dependent studies that revealed no cluster agglomeration up to 350 °C in vacuo. Furthermore, stable, confined Au clusters were produced via an original atomicity-preserving ligand-stripping procedure by taking advantage of phosphine oxidation. Thus, capitalising on ZIF-8 hosting ability for metal nanoclusters while exploiting confined space for activation delivers a promising way towards producing and studying atom-precise clusters.

中文翻译：

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通过 ZIF-8 封装从磷化氢稳定到裸露的 Au8 簇

与相应的惰性块状材料相比，纳米级金簇具有显着的光学和催化特性，这些特性高度依赖于簇的大小。金属有机框架（MOF）由于其有限的多孔环境，最近被确定为金属簇的有吸引力的主体基质。通过磺化配体的合理选择，我们首次报道了膦稳定的 Au ₈簇通过以下方式封装到 ZIF-8 中一种瓶装船方法。MOF 内的簇完整性已通过全面表征证明，包括漫反射紫外-可见光谱和具有元素映射的高分辨率透射电子显微镜。这种策略能够精确控制从低 (1.1 wt% Au) 到高 (8.2 wt% Au) 值的簇负载。MOF 提供的稳定作用在温度依赖性研究中得到进一步分析，结果表明在真空中高达 350°C 没有团簇团聚。此外，稳定、受限的 Au 簇是通过利用膦氧化的原始原子保留配体剥离程序。因此，利用 ZIF-8 对金属纳米团簇的承载能力，同时利用密闭空间进行活化，为生产和研究原子精确团簇提供了一种有前途的方法。