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

Yaxing Wang; Linjuan Zhang; Lanhua Chen; Weifeng Li; Xing Dai; Juan Diwu; Jianqiang Wang; Zhifang Chai; Shuao Wang

doi:10.1021/acs.inorgchem.6b02010

Th(H₂O)(I^VO₃)₂[I^VII_0.6V_1.76O₇(OH)]: A Mixed-Valent Iodine Compound Containing Periodate Stabilized by Crystallographically Compatible Lattice Sites

Inorg Chem. 2016 Dec 5;55(23):12101-12104. doi: 10.1021/acs.inorgchem.6b02010. Epub 2016 Nov 17.

Authors

Yaxing Wang^{1

2}, Linjuan Zhang³, Lanhua Chen^{1

2}, Weifeng Li^{1

2}, Xing Dai^{1

2}, Juan Diwu^{1

2}, Jianqiang Wang³, Zhifang Chai^{1

2}, Shuao Wang^{1

2}

Affiliations

¹ School for Radiological and Interdisciplinary Sciences (RAD-X), Soochow University , 199 Renai Road, Suzhou Industrial Park, China.
² Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions , 199 Renai Road, Suzhou Industrial Park, China.
³ Shanghai Institute of Applied Physics, Chinese Academy of Sciences , 2019 JiaLuo Road, Shanghai 201800, China.

PMID: 27934441
DOI: 10.1021/acs.inorgchem.6b02010

Abstract

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.