Th(H2O)(IVO3)2[IVII0.6V1.76O7(OH)]: A Mixed-Valent Iodine Compound Containing Periodate Stabilized by Crystallographically Compatible Lattice Sites.
Th(H2O)(IVO3)2[IVII0.6V1.76O7(OH)]: A Mixed-Valent Iodine Compound Containing Periodate Stabilized by Crystallographically Compatible Lattice Sites.
复制标题
DOI：
10.1021/acs.inorgchem.6b02010
复制
发表时间：
2016-11
影响因子：
4.6
通讯作者：
Yaxing Wang;Lin-juan Zhang;Lanhua Chen;Weifeng Li;Xing Dai;Juan Diwu;Jianqiang Wang;Z. Chai;Shuao Wang
中科院分区：
文献类型：
--
作者：
Yaxing Wang;Lin-juan Zhang;Lanhua Chen;Weifeng Li;Xing Dai;Juan Diwu;Jianqiang Wang;Z. Chai;Shuao Wang
高碘酸盐是一种强氧化剂，通常在水热条件下还原为IO 3-或I2。在这里，我们提出了一个罕见的混合价碘酸盐（V）/高碘酸盐（VII）的化合物，Th（H2O）（IVO 3）2[IVII0.6V1.76O7（OH）]，水热法制备从高碘酸。晶体学结果表明，七价碘采用IVIIO 6扭曲的八面体几何形状，这是稳定的晶体相容的晶格位置的VO 6八面体通过异价取代无序机制。X射线光电子和同步辐射X射线吸收光谱仪均定量证实存在摩尔比（IV/IVII）为4：1的混合价碘含氧阴离子，与单晶X射线分析一致。具有相容晶格位置的混合价产物的结晶可以被巧妙地用于稳定一般其他元素的不寻常氧化态。
Periodate is a strong oxidant and is often reduced to IO3- or I2 under hydrothermal conditions. Here, we present a rare case of a mixed-valent iodate(V)/periodate(VII) compound, Th(H2O)(IVO3)2[IVII0.6V1.76O7(OH)], prepared with a hydrothermal method starting from periodic acid. Crystallographic results demonstrate that heptavalent iodine adopts IVIIO6 distorted octahedral geometries, which are stabilized on the crystallographically compatible crystal lattice sites of VO6 octahedra through an aliovalent substitutional disorder mechanism. X-ray photoelectron and synchrotron radiation X-ray absorption spectroscopes both quantitatively confirm the presence of mixed valent iodine oxoanions with a molar ratio (IV/IVII) of 4:1, consistent with the single crystal X-ray analysis. The crystallization of mixed-valent products with compatible lattice site can be fancily utilized for stabilizing the uncommon oxidation states of other elements in general.