Th(H2O)(IVO3)2[IVII0.6V1.76O7(OH)]: A Mixed-Valent Iodine Compound Containing Periodate Stabilized by Crystallographically Compatible Lattice Sites

详细信息    查看全文

• 作者：Yaxing Wang ; Linjuan Zhang ; Lanhua Chen ; Weifeng Li ; Xing Dai ; Juan Diwu ; Jianqiang Wang ; Zhifang Chai ; Shuao Wang
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：December 5, 2016
• 年：2016
• 卷：55
• 期：23
• 页码：12101-12104
• 全文大小：255K
• ISSN：1520-510X

文摘

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)(I^VO₃)₂[I^VII_0.6V_1.76O₇(OH)], prepared with a hydrothermal method starting from periodic acid. Crystallographic results demonstrate that heptavalent iodine adopts I^VIIO₆ 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 (I^V/I^VII) 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.