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Magnetic Structure and Exchange Interactions in Quasi-One-Dimensional MnCl2(urea)2.


ABSTRACT: MnCl2(urea)2 is a new linear chain coordination polymer that exhibits slightly counter-rotated Mn2Cl2 rhomboids along the chain-axis. The material crystallizes in the noncentrosymmetric orthorhombic space group Iba2, with each Mn(II) ion equatorially surrounded by four Cl(-) that lead to bibridged ribbons. Urea ligands coordinate via O atoms in the axial positions. Hydrogen bonds of the Cl···H-N and O···H-N type link the chains into a quasi-3D network. Magnetic susceptibility data reveal a broad maximum at 9 K that is consistent with short-range magnetic order. Pulsed-field magnetization measurements conducted at 0.6 K show that a fully polarized magnetic state is achieved at Bsat = 19.6 T with another field-induced phase transition occurring at 2.8 T. Zero-field neutron diffraction studies made on a powdered sample of MnCl2(urea)2 reveal that long-range magnetic order occurs below TN = 3.2(1) K. Additional Bragg peaks due to antiferromagnetic (AFM) ordering can be indexed according to the Ib'a2' magnetic space group and propagation vector ? = [0, 0, 0]. Rietveld profile analysis of these data revealed a Néel-type collinear ordering of Mn(II) ions with an ordered magnetic moment of 4.06(6) ?B (5 ?B is expected for isotropic S = (5)/2) oriented along the b-axis, i.e., perpendicular to the chain-axis that runs along the c-direction. Owing to the potential for spatial exchange anisotropy and the pitfalls in modeling bulk magnetic data, we analyzed inelastic neutron scattering data to retrieve the exchange constants: Jc = 2.22 K (intrachain), Ja = -0.10 K (interchain), and D = -0.14 K with J > 0 assigned to AFM coupling. This J configuration is most unusual and contrasts the more commonly observed AFM interchain coupling of 1D chains.

SUBMITTER: Manson JL 

PROVIDER: S-EPMC4784262 | biostudies-literature | 2015 Dec

REPOSITORIES: biostudies-literature

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Magnetic Structure and Exchange Interactions in Quasi-One-Dimensional MnCl2(urea)2.

Manson Jamie L JL   Huang Qing-Zhen QZ   Brown Craig M CM   Lynn Jeffrey W JW   Stone Matthew B MB   Singleton John J   Xiao Fan F  

Inorganic chemistry 20151208 24


MnCl2(urea)2 is a new linear chain coordination polymer that exhibits slightly counter-rotated Mn2Cl2 rhomboids along the chain-axis. The material crystallizes in the noncentrosymmetric orthorhombic space group Iba2, with each Mn(II) ion equatorially surrounded by four Cl(-) that lead to bibridged ribbons. Urea ligands coordinate via O atoms in the axial positions. Hydrogen bonds of the Cl···H-N and O···H-N type link the chains into a quasi-3D network. Magnetic susceptibility data reveal a broad  ...[more]

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