The [U2(μ-S2)2Cl8]4- Anion: Synthesis and Characterization of the Uranium Double Salt Cs5[U2(μ-S2)2Cl8]I

Matthew D. Ward; Eric A. Pozzi; Minseong Lee; Richard P. Van Duyne; Eun Sang Choi; James A. Ibers

doi:10.1021/acs.inorgchem.5b00234

The [U₂(μ-S₂)₂Cl₈]^4- Anion: Synthesis and Characterization of the Uranium Double Salt Cs₅[U₂(μ-S₂)₂Cl₈]I

Matthew D. Ward, Eric A. Pozzi, Minseong Lee, Richard P. Van Duyne, Eun Sang Choi, James A. Ibers^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Red plates of Cs₅[U₂(μ-S₂)₂Cl₈]I were obtained in good yield from the reaction at 1173 K of U, GeI₂ or SnI₄, and S, with CsCl flux. The compound crystallizes in space group D2h25-Immm of the orthorhombic system in the Cs₅[Nb₂(μ-S₂)₂Cl₈]Cl structure type. The centrosymmetric [U₂(μ-S₂)₂Cl₈]^4- anion in the structure has mmm symmetry with the two U⁴⁺ atoms separated by 3.747(1) Å. Each U atom is coordinated to four Cl atoms and four S atoms from two S₂^2- groups in a square-antiprismatic arrangement. The polarized absorbance spectra of Cs₅[U₂(μ-S₂)₂Cl₈]I display prominent optical anisotropy. Magnetic measurements are consistent with the modified Curie-Weiss law at high temperatures. The low-temperature behavior may arise from antiferromagnetic coupling of the U⁴⁺ ions within the anion.

Original language	English (US)
Pages (from-to)	3055-3060
Number of pages	6
Journal	Inorganic chemistry
Volume	54
Issue number	6
DOIs	https://doi.org/10.1021/acs.inorgchem.5b00234
State	Published - Mar 16 2015

ASJC Scopus subject areas

Inorganic Chemistry
Physical and Theoretical Chemistry

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title = "The [U2(μ-S2)2Cl8]4- Anion: Synthesis and Characterization of the Uranium Double Salt Cs5[U2(μ-S2)2Cl8]I",

abstract = "Red plates of Cs5[U2(μ-S2)2Cl8]I were obtained in good yield from the reaction at 1173 K of U, GeI2 or SnI4, and S, with CsCl flux. The compound crystallizes in space group D2h25-Immm of the orthorhombic system in the Cs5[Nb2(μ-S2)2Cl8]Cl structure type. The centrosymmetric [U2(μ-S2)2Cl8]4- anion in the structure has mmm symmetry with the two U4+ atoms separated by 3.747(1) {\AA}. Each U atom is coordinated to four Cl atoms and four S atoms from two S22- groups in a square-antiprismatic arrangement. The polarized absorbance spectra of Cs5[U2(μ-S2)2Cl8]I display prominent optical anisotropy. Magnetic measurements are consistent with the modified Curie-Weiss law at high temperatures. The low-temperature behavior may arise from antiferromagnetic coupling of the U4+ ions within the anion.",

author = "Ward, {Matthew D.} and Pozzi, {Eric A.} and Minseong Lee and {Van Duyne}, {Richard P.} and Choi, {Eun Sang} and Ibers, {James A.}",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2015",

month = mar,

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doi = "10.1021/acs.inorgchem.5b00234",

language = "English (US)",

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AU - Ward, Matthew D.

AU - Pozzi, Eric A.

AU - Lee, Minseong

AU - Van Duyne, Richard P.

AU - Choi, Eun Sang

AU - Ibers, James A.

PY - 2015/3/16

Y1 - 2015/3/16

N2 - Red plates of Cs5[U2(μ-S2)2Cl8]I were obtained in good yield from the reaction at 1173 K of U, GeI2 or SnI4, and S, with CsCl flux. The compound crystallizes in space group D2h25-Immm of the orthorhombic system in the Cs5[Nb2(μ-S2)2Cl8]Cl structure type. The centrosymmetric [U2(μ-S2)2Cl8]4- anion in the structure has mmm symmetry with the two U4+ atoms separated by 3.747(1) Å. Each U atom is coordinated to four Cl atoms and four S atoms from two S22- groups in a square-antiprismatic arrangement. The polarized absorbance spectra of Cs5[U2(μ-S2)2Cl8]I display prominent optical anisotropy. Magnetic measurements are consistent with the modified Curie-Weiss law at high temperatures. The low-temperature behavior may arise from antiferromagnetic coupling of the U4+ ions within the anion.

AB - Red plates of Cs5[U2(μ-S2)2Cl8]I were obtained in good yield from the reaction at 1173 K of U, GeI2 or SnI4, and S, with CsCl flux. The compound crystallizes in space group D2h25-Immm of the orthorhombic system in the Cs5[Nb2(μ-S2)2Cl8]Cl structure type. The centrosymmetric [U2(μ-S2)2Cl8]4- anion in the structure has mmm symmetry with the two U4+ atoms separated by 3.747(1) Å. Each U atom is coordinated to four Cl atoms and four S atoms from two S22- groups in a square-antiprismatic arrangement. The polarized absorbance spectra of Cs5[U2(μ-S2)2Cl8]I display prominent optical anisotropy. Magnetic measurements are consistent with the modified Curie-Weiss law at high temperatures. The low-temperature behavior may arise from antiferromagnetic coupling of the U4+ ions within the anion.

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The [U₂(μ-S₂)₂Cl₈]^4- Anion: Synthesis and Characterization of the Uranium Double Salt Cs₅[U₂(μ-S₂)₂Cl₈]I

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