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Title: Magnetic Structure and Exchange Interactions in Quasi-One-Dimensional MnCl 2(urea) 2

Abstract

MnCl 2(urea) 2 is a new linear chain coordination polymer that exhibits slightly counter-rotated Mn 2Cl 2 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 B sat = 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 MnCl 2(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 τ = [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) μB (5 μB is expected for isotropic S = 5/2)more » 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.« less

Authors:
 [1];  [2];  [3];  [2];  [4]; ORCiD logo [5];  [6]
  1. Eastern Washington University, Cheney, WA (United States)
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Delaware, Newark, DE (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  6. Durham Univ. (United Kingdom)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1457261
Alternate Identifier(s):
OSTI ID: 1528743
Report Number(s):
LA-UR-15-27162
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
AC52-06NA25396; AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 24; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Manson, Jamie L., Huang, Qing-zhen, Brown, Craig M., Lynn, Jeffrey W., Stone, Matthew B., Singleton, John, and Xiao, Fan. Magnetic Structure and Exchange Interactions in Quasi-One-Dimensional MnCl2(urea)2. United States: N. p., 2015. Web. doi:10.1021/acs.inorgchem.5b02162.
Manson, Jamie L., Huang, Qing-zhen, Brown, Craig M., Lynn, Jeffrey W., Stone, Matthew B., Singleton, John, & Xiao, Fan. Magnetic Structure and Exchange Interactions in Quasi-One-Dimensional MnCl2(urea)2. United States. https://doi.org/10.1021/acs.inorgchem.5b02162
Manson, Jamie L., Huang, Qing-zhen, Brown, Craig M., Lynn, Jeffrey W., Stone, Matthew B., Singleton, John, and Xiao, Fan. Tue . "Magnetic Structure and Exchange Interactions in Quasi-One-Dimensional MnCl2(urea)2". United States. https://doi.org/10.1021/acs.inorgchem.5b02162. https://www.osti.gov/servlets/purl/1457261.
@article{osti_1457261,
title = {Magnetic Structure and Exchange Interactions in Quasi-One-Dimensional MnCl2(urea)2},
author = {Manson, Jamie L. and Huang, Qing-zhen and Brown, Craig M. and Lynn, Jeffrey W. and Stone, Matthew B. and Singleton, John and Xiao, Fan},
abstractNote = {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 τ = [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) μB (5 μB 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.},
doi = {10.1021/acs.inorgchem.5b02162},
url = {https://www.osti.gov/biblio/1457261}, journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 24,
volume = 54,
place = {United States},
year = {2015},
month = {12}
}

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