Insights into the Self-Assembly Mechanism of the Modular Polyoxometalate "Keggin-Net" Family of Framework Materials and Their Electronic Properties
Insights into the Self-Assembly Mechanism of the Modular Polyoxometalate "Keggin-Net" Family of Framework Materials and Their Electronic Properties
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DOI：
10.1021/cg201342z
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发表时间：
2012-01
影响因子：
3.8
通讯作者：
J. Thiel;P. Molina;M. Symes;L. Cronin
中科院分区：
文献类型：
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作者：
J. Thiel;P. Molina;M. Symes;L. Cronin
已经检查了仅基于多金属氧酸盐 Keggin 簇的无机骨架材料的合成机理，并研究了它们的电子特性。分子式为 (C4H10NO)n[W72M12O268X7]（杂原子 X = Si 或 Ge，异金属 M = Co(II) 或 Mn(III)）的模块化网络化合物的组装基于亚稳态前体材料 [γ-XW10O36]8– 的异构化，然后包含异金属并随后组装成扩展的框架结构。以锰取代为特征的两种框架可以在再结晶过程中分解和重新组装，而钴版本则没有表现出类似的行为。四种化合物在杂原子和杂金属取代方面的内在差异体现在它们的氧化还原行为上。
The mechanism for the syntheses of inorganic framework materials based solely on polyoxometalate Keggin clusters has been examined and their electronic properties have been investigated. The assembly of the modular network compounds with the molecular formula (C4H10NO)n[W72M12O268X7] (with the heteroatom X = Si or Ge and the heterometal M = Co(II) or Mn(III)) is based on the isomerization of the metastable precursor material [γ-XW10O36]8–, followed by the inclusion of the heterometal and subsequent assembly into the extended framework structure. The two frameworks featuring manganese substitution can be dis- and reassembled in a recrystallization process while the cobalt versions do not show comparable behavior. The intrinsic differences of the four compounds with regards to their heteroatom and heterometal substitution are shown in terms of their redox behavior.