The success and continued expansion of research on metal-oxo clusters owe largely to their structural richness and wide range of functions. However, while most of them known to date are negatively charged polyoxometalates, there is only a handful of cationic ones, much less functional ones. Here, we show an all-inorganic hydroxyiodide [H 10.7 Sb 32.1 O 44 ][H 2.1 Sb 2.1 I 8 O 6 ][Sb 0.76 I 6 ] 2 ·25H 2 O ( HSbOI ), forming a face-centered cubic structure with cationic Sb 32 O 44 clusters and two types of anionic clusters in its interstitial spaces. Although it is submicrometer in size, electron diffraction tomography of HSbOI allowed the construction of the initial structural model, followed by powder Rietveld refinement to reach the final structure. The cationic cluster is characterized by the presence of acidic protons on its surface due to substantial Sb 3+ deficiencies, which enables HSbOI to serve as an excellent solid acid catalyst. These results open up a frontier for the exploration and functionalization of cationic metal-oxo clusters containing heavy main group elements.

中文翻译：

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具有酸性质子的多氧阳离子氧化锑簇

金属氧簇研究的成功和持续扩展在很大程度上归功于它们的结构丰富性和广泛的功能。然而，虽然迄今为止已知的大多数是带负电的多金属氧酸盐，但只有少数阳离子，更不用说功能性的了。在这里，我们展示了一种全无机羟基碘化物 [H10.7锑32.1○44][H2.1锑2.1我8○6][锑0.76我6]2·25小时2O ( HSbOI )，与阳离子 Sb 形成面心立方结构32○44簇和两种类型的阴离子簇在其间隙空间中。虽然它的尺寸是亚微米，但 HSbOI 的电子衍射断层扫描允许构建初始结构模型，然后进行粉末 Rietveld 细化以达到最终结构。阳离子簇的特征是由于大量的 Sb 在其表面存在酸性质子3+缺陷，这使得 HSbOI 能够作为一种优异的固体酸催化剂。这些结果为含有重主族元素的阳离子金属氧簇的探索和功能化开辟了前沿。