Chen Man-Ting, Xu Qiao-Fei, Aibibula Mukeremu, Kong Xiang-Jian, Long La-Sheng, Zheng Lan-Sun
State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
J Am Chem Soc. 2024 Aug 14;146(32):22134-22139. doi: 10.1021/jacs.4c07231. Epub 2024 Jul 31.
Open hollow dodecahedral cage clusters have long been a coveted target in synthetic chemistry, yet their creation poses immense challenges. Here we report two open hollow dodecahedral lanthanide-aluminum (Ln-Al) heterometallic cage clusters, namely, LnAl(μ-OH)(μ-OH)(OAc)(HO)·(MeCN)·(HO), (Ln = Dy and = 27, = 300 for ; Ln = Y and = 28, = 420 for ). Remarkably, the 350 metal atoms in and display a Keplerate-type four-shell structure of truncated icosidodecahedron@dodecahedron@dodecahedron@icosidodecahedron. The diameter of the cationic cluster in is approximately 5.0 nm, with an inner cavity diameter of about 2.8 nm and a window diameter of roughly 0.66 nm. The cluster in boasts an accessible inner void volume of up to 15,000 Å. Notably, these cage clusters maintain stability in water, and the truncated icosidodecahedrons in and are the first of their kind synthesized to date. Given that the open hollow dodecahedral Ln-Al cage cluster has never been reported before, this work represents a member in the family of hollow open dodecahedral cages.
开放的空心十二面体笼状簇长期以来一直是合成化学中令人垂涎的目标，但其合成面临巨大挑战。在此，我们报道了两种开放的空心十二面体镧系 - 铝（Ln - Al）异金属笼状簇，即LnAl(μ - OH)(μ - OH)(OAc)(HO)·(MeCN)·(HO)，（Ln = Dy时 = 27， = 300；Ln = Y时 = 28， = 420）。值得注意的是， 和 中的350个金属原子呈现出截角二十面体@十二面体@十二面体@二十面体的开普勒型四壳结构。 中阳离子簇的直径约为5.0 nm，内腔直径约为2.8 nm，窗口直径约为0.66 nm。 中的簇具有高达15,000 Å的可及内部空隙体积。值得注意的是，这些笼状簇在水中保持稳定，并且 和 中的截角二十面体是迄今为止首次合成的此类结构。鉴于此前从未报道过开放的空心十二面体Ln - Al笼状簇，这项工作代表了空心开放十二面体笼家族中的一员。
