A giant polyaluminum species S-Al32 and two aluminum polyoxocations involving coordination by sulfate ions S-Al32 and S-K-Al13.
A giant polyaluminum species S-Al32 and two aluminum polyoxocations involving coordination by sulfate ions S-Al32 and S-K-Al13.
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DOI：
10.1021/ic101875r
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发表时间：
2011-01
影响因子：
4.6
通讯作者：
Zhong Sun;Hui Wang;H. Tong;Shaofan Sun
中科院分区：
文献类型：
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作者：
Zhong Sun;Hui Wang;H. Tong;Shaofan Sun
[Al32O8(OH)60(H2O)28(SO4)2](16+) （S- al32）和[Al13O4(OH)25(H2O)10(SO4)](4+) (S- k - al13) [S]表明硫酸盐离子参与了铝多阳离子的配位；K代表Keggin结构]分别在[Al32O8(OH)60(H2O)28(SO4)2][SO4]7[Cl]2·30H2O和[Al13O4(OH)25(H2O)10(SO4)]4[SO4]8·20H2O的结构中得到。它们是由硫酸盐离子配位的前两种铝多氧化位。S-Al32的“核壳”结构与Al30相似，但单元由两个[Al(OH)2(H2O)3(SO4)]（-）基团连接，取代了四个η(1)-H2O分子。S-K-Al13的结构与我们熟知的ε-K-Al13的结构相似，但其单元由两个（SO4(2-)）0.5连接，并替换了一个h30（+）离子。结果表明，多氧化位与反离子之间存在很强的相互作用。根据它们的结构特征和制备条件，提出了ε-K-Al13到S-K-Al13和S-Al32的形成演化机制。通过对多阳离子中各中心Al（3+）离子局部碱化度计算结果的比较，提取了局部碱化度对称均衡原理。它们可以用来解释两种铝是如何形成和演化的，为什么硫酸盐离子可以与它们协调，并预测oh桥接位置在进一步水解时的位置。
The giant polyaluminum species [Al32O8(OH)60(H2O)28(SO4)2](16+) (S-Al32) and [Al13O4(OH)25(H2O)10(SO4)](4+) (S-K-Al13) [S means that sulfate ions take part in coordination of the aluminum polycation; K represents the Keggin structure] were obtained in the structures of [Al32O8(OH)60(H2O)28(SO4)2][SO4]7[Cl]2·30H2O and [Al13O4(OH)25(H2O)10(SO4)]4[SO4]8·20H2O, respectively. They are the first two aluminum polyoxocations coordinated by sulfate ions. The "core-shell" structure of S-Al32 is similar to that of Al30, but the units are linked by two [Al(OH)2(H2O)3(SO4)](-) groups with replacement of four η(1)-H2O molecules. The structure of S-K-Al13 is similar to the well-known structure of ε-K-Al13, but the units are linked by two (SO4(2-))0.5 with replacement of a H3O(+) ion. It was shown that strong interaction exists between the polyoxocations and counterions. On the basis of their structural features and preparation conditions, a formation and evolution mechanism (from ε-K-Al13 to S-K-Al13 and S-Al32) has been proposed. A local basification degree symmetrical equalization principle was extracted based on a comparison of the calculated results of the local basification degree for each central Al(3+) ion included in a polycation. They can be used to explain how the two aluminum species are formed and evolved and why the sulfate ions can coordinate to them and to predict where the OH-bridging positions will be upon further hydrolysis.