Magnetic studies on hexaiodrohenate (IV) salts of univalent cations. Spin canting and magnetic ordering in K-2 [Rel(6)]with T-c=24 K

Dublin Core

Title

Magnetic studies on hexaiodrohenate (IV) salts of univalent cations. Spin canting and magnetic ordering in K-2 [Rel(6)]with T-c=24 K

Subject

ESTRUCTURA CRISTALINA
RENIO
BIBLIOGRAFIA NACIONAL QUIMICA

Abstract

The ionic salts of rhenium(IV) of formula (Cat)2[ReI6] with Cat ) Li+ (1), Na+ (2), K+ (3), Rb+ (4), Cs+ (5), NH4 + (6), and AsPh4 + (7) [AsPh4 + ) tetraphenylarsonium cation] have been synthesized, and the structures of two of them (namely, 3 and 6) were determined by single-crystal X-ray diffraction. 3 crystallizes in the monoclinic system, space group Pn, with a ) 7.815(1) Å, b ) 7.874(1) Å, c ) 11.335(1) Å, â ) 90.38(1)°, and Z ) 2 whereas 6 crystallizes in the tetragonal system, space group P4/mnc, with a ) 7.881(1) Å, b ) 7.881(1) Å, c ) 11.474(2) Å, and Z ) 2. The structures of 3 and 6 are made up of discrete [ReI6]2- anions and K+ (3) or NH4 + (6) cations held together by electrostatic forces (3 and 6) and N-HâââI hydrogen bonds (6). The rhenium(IV) cation in 3 and 6 is surrounded by six iodide ligands in an octahedral environment with the Re-I bond lengths varying in a very narrow range [2.704(3)-2.738(3) and 2.716(1)-2.722(2) Å for 3 and 6, respectively]. The [ReI6]2- anions in 6 describe a tetragonally distorted body-centered cubic structure. In 3, the arrangement of these units is similar but more distorted. The different arrangement of the anions in 3 and 6 accounts for the centrosymmetric (6) and non-centrosymmetric (3) structures observed. The magnetic properties of 1-7 were investigated in the temperature range 2.0-300 K. The magnetic behavior of 7 is that of a magnetically diluted Re(IV) complex with a large value of the zero-field splitting of the ground level (j2Dj ) 49.8 cm-1) whereas those of 1, 2, and 4-6 are typical of antiferromagnetically coupled systems with susceptibility maxima at 28 (1), 27 (2), 21 (4), 16 (5), and 20 K (6). In the case of compound 3, its magnetic behavior in the high-temperature range is parallel to that observed in the parent salts but below 24 K it is a weak ferromagnet with a canting angle of ca. 1.2°.

Creator

De Munno, G.
Nicolo, F.
Lloret, F
Julve, M.
Faus, J.

Source

Inorganic Chemistry v. 42, no. 8, 2003. -- p. 2512-2518

Publisher

American Chemical Society

Date

2003

Rights

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Format

PDF

Language

Inglés

Type

Artículo

Identifier

DOI: 10.1021/ic020531j
Date Added
March 2, 2015
Collection
Bibliografía Nacional Química
Item Type
Document
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Citation
Gonzalez, Ricardo et al., “Magnetic studies on hexaiodrohenate (IV) salts of univalent cations. Spin canting and magnetic ordering in K-2 [Rel(6)]with T-c=24 K,” RIQUIM - Repositorio Institucional de la Facultad de Química - UdelaR, accessed November 17, 2025, https://riquim.fq.edu.uy/items/show/2446.