title: Two-Dimensional Inorganic Cationic Network of Thorium Iodate Chloride with Unique Halogen-Halogen Bonds.
abstract: A unique two-dimensional inorganic cationic network with the formula [Th3O2(IO3)5(OH)2]Cl was synthesized hydrothermally. Its crystal structure can best be described as positively charged slabs built with hexanuclear thorium clusters connected by iodate trigonal pyramids. Additional chloride anions are present in the interlayer spaces but surprisingly are not exchangeable, as demonstrated by a series of CrO4(2-) uptake experiments. This is because all chloride anions are trapped by multiple strong halogen-halogen interactions with short Cl-I bond lengths ranging from 3.134 to 3.333 Å, forming a special Cl-centered trigonal-pyramidal polyhedron as a newly observed coordination mode for halogen bonds. Density functional theory calculations clarified that electrons transformed from central Cl atoms to I atoms, generating a halogen-halogen interaction energy with a value of about -8.3 kcal mol(-1) per Cl···I pair as well as providing a total value of -57.9 kcal mol(-1) among delocalized halogen-halogen bonds, which is a new record value reported for a single halogen atom. Additional hydrogen-bonding interaction is also present between Cl and OH, and the interaction energy is predicted to be -8.1 kcal mol(-1), confirming the strong total interaction to lock the interlayer Cl anions.
authors: Huangjie
authors: H
authors: Lu
authors: Yaxing
authors: Y
authors: Wang
authors: Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences , Beijing 100049, China.
authors: Congzhi
authors: C
authors: Wang
authors: Lanhua
authors: L
authors: Chen
authors: Laboratory of Nuclear Energy Chemistry and Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences , Beijing 100049, China.
authors: Weiqun
authors: W
authors: Shi
authors: Juan
authors: J
authors: Diwu
authors: Zhifang
authors: Z
authors: Chai
authors: Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306, United States.
authors: Thomas E
authors: TE
authors: Albrecht-Schmitt
authors: Shuao
authors: S
authors: Wang