A. V. Konkova, D. V. Evtushok, Y. A. Vorotnikov, I. V. Eltsov, V. V. Yanshole, A. A. Ivanov, M. A. Shestopalov
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引用次数: 0
摘要
摘要 在 Bu4NOH 的水溶液中，用四丁基铵在沸腾状态下对 (NH4)4[Mo12O28(μ-L)8]（L = pz（吡唑酸盐）和 trz（1,2,4-三唑酸盐））中的铵阳离子进行了偏析。通过 XRD、1H NMR 和质谱等多种物理化学方法证实了阳离子的取代和阴离子团簇片段的保留。所得到的化合物在有机溶剂中易溶且稳定，因此对其氧化还原特性进行了研究。根据循环伏安数据，L = pz 和 trz 时，化合物表现出 E1/2 = 0.26 V 和 0.61 V 的可逆氧化性。量子化学计算对电子结构进行了研究。结果表明，这些化合物的前沿分子轨道主要由钼 d 轨道组成。
Tetrabutylammonium Salts of [Mo12O28(μ-L)8]4– Polyoxometal Clusters with Pyrazolate and Triazolate Ligands
The metathesis of ammonium cations in (NH4)4[Mo12O28(μ-L)8] (L = pz (pyrazolate) and trz (1,2,4-triazolate)) with tetrabutylammonium is performed under boiling in an aqueous solution with Bu4NOH. The substitution of cations and the preservation of the anionic cluster fragment are confirmed by a number of physicochemical methods such as XRD, 1H NMR, and mass spectrometry. The resulting compounds are soluble and stable in organic solvents, so their redox properties are studied. According to the cyclic voltammetry data, the compounds exhibit reversible oxidation with E1/2 = 0.26 V and 0.61 V for L = pz and trz respectively. The electronic structure is studied by quantum chemical calculations. It is shown that the frontier molecular orbitals of these compounds are mainly composed of molybdenum d-orbitals.
期刊介绍：
Journal is an interdisciplinary publication covering all aspects of structural chemistry, including the theory of molecular structure and chemical bond; the use of physical methods to study the electronic and spatial structure of chemical species; structural features of liquids, solutions, surfaces, supramolecular systems, nano- and solid materials; and the crystal structure of solids.
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