类葫芦素巨型聚硫代氧酸盐：结构分析与溶液研究

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-02-17 DOI:10.1021/acs.inorgchem.4c05330

Jérôme Marrot, Clément Falaise, Maya Abou Fadel, Nathalie Leclerc, Mohamed Haouas, Sébastien Floquet, Francis Sécheresse, Emmanuel Cadot

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引用次数: 0

摘要

金属酸盐离子在双核连接剂{Mo2E2S2}2+ （E = O， S）和弱螯合配体（如乙酸或硫酸盐）存在下的缩聚过程导致巨大的多金属酸盐物种，通过五边形金属-氧单元的连接组装。虽然最流行的结构原型无疑是keplerate型胶囊，在拓扑结构上让人联想到富勒烯C60，但我们在这里报告了一种新的巨型多氧硫金属酸盐的形成条件，其大圆柱形类似于有机瓜脲。[(SO4)20(H120W80Mo40S40O360)]40 -阴离子被分离成适合x射线衍射分析的单晶，突出了葫芦素样组装体的大尺寸，其长度达到24 Å，直径达到14 Å。通过拉曼光谱、紫外-可见光谱和小角x射线散射研究了该巨聚阴离子的溶液行为，表明其在水溶液中保持了结构。这些总体结果在超分子化学领域开辟了相关的前景。

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Cucurbituril-like Giant PolyOxoThiometalate: Structural Analysis and Solution Studies

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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.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

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.