Jérôme Marrot*, Clément Falaise, Maya Abou Fadel, Nathalie Leclerc, Mohamed Haouas, Sébastien Floquet, Francis Sécheresse and Emmanuel Cadot*,
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引用次数: 0
摘要
金属酸根离子在双核连接体 {Mo2E2S2}2+（E = O、S）和弱螯合配体（如醋酸盐或硫酸盐）存在下的缩聚过程会产生巨大的多氧金属酸根物种，这些物种通过五边形金属氧单元的连接组装而成。虽然最流行的结构原型无疑是开普勒型胶囊，从拓扑学上看与富勒烯 C60 相似，但我们在此报告了一种新的巨型多氧硫代金属酸盐的形成条件，其大圆柱形类似于有机葫芦素。我们分离出了[(SO4)20(H120W80Mo40S40O360)]40-阴离子单晶体，并对其进行了 X 射线衍射分析。拉曼光谱、紫外-可见光谱和小角 X 射线散射研究了这种巨大多负离子的溶液行为，发现其结构在水溶液中保持不变。这些总体结果为超分子化学领域开辟了相关前景。
Cucurbituril-like Giant PolyOxoThiometalate: Structural Analysis and Solution Studies
Polycondensation processes of metalate ions in the presence of a dinuclear linker {Mo2E2S2}2+ (E = O, S) and weakly chelating ligands such as acetate or sulfate lead to giant polyoxometalate species, assembled through the connection of pentagonal metal-oxo units. While the most popular structural archetype is undoubtedly the Keplerate-type capsule, topologically reminiscent of the fullerene C60, we report here on the formation conditions of a new giant polyoxothiometalate, whose large cylindrical shape resembles that of organic cucurbituril. The [(SO4)20(H120W80Mo40S40O360)]40– anion has been isolated as single crystals suitable for X-ray diffraction analysis, highlighting the large dimensions of the cucurbituril-like assembly, which reaches 24 Å in length and 14 Å in diameter. The solution behavior of this gigantic polyanion was investigated by Raman, UV–vis spectroscopy, and small-angle X-ray scattering, revealing that its structure is maintained in aqueous solution. These overall results open relevant perspectives in the field of supramolecular chemistry.
期刊介绍：
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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