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Title: Antiferromagnetism in a Family of S = 1 Square Lattice Coordination Polymers NiX 2 (pyz) 2 (X = Cl, Br, I, NCS; pyz = Pyrazine)

Abstract

The crystal structures of NiX2(pyz)(2) (X = Cl (1), Br (2), I (3), and NCS (4)) were determined by synchrotron X-ray powder diffraction. All four compounds consist of two-dimensional (2D) square arrays self-assembled from octahedral NiN4X2 units that are bridged by pyz ligands. The 2D layered motifs displayed by 1-4 are relevant to bifluoride-bridged [Ni(HF2) (pyz)(2)]EF6 (E = P, Sb), which also possess the same 2D layers. In contrast, terminal X ligands occupy axial positions in 1-4 and cause a staggered packing of adjacent layers. Long-range antiferromagnetic (AFM) order occurs below 1.5 (Cl), 1.9 (Br and NCS), and 2.5 K (I) as determined by heat capacity and muon-spin relaxation. The single-ion anisotropy and g factor of 2, 3, and 4 were measured by electron-spin resonance with no evidence for zero field splitting (ZFS) being observed. The magnetism of 1-4 spans the spectrum from quasi-two-dimensional (2D) to three-dimensional (3D) antiferromagnetism. Nearly identical results and thermodynamic features were obtained for 2 and 4 as shown by pulsed-field magnetization, magnetic susceptibility, as well as their Neel temperatures. Magnetization curves for 2 and 4 calculated by quantum Monte Carlo simulation also show excellent agreement with the pulsed-field data. Compound 3 is characterized as amore » 3D AFM with the interlayer interaction (j(perpendicular to)) being slightly stronger than the intralayer interaction along Ni-pyz-Ni segments (j(pyz)) within the two-dimensional [Ni(pyz)(2)](2+) square planes. Regardless of X, j(pyz), is similar for the four compounds and is roughly 1 K.« less

Authors:
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Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1392921
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 55; Journal Issue: 7; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Liu, Junjie, Goddard, Paul A., Singleton, John, Brambleby, Jamie, Foronda, Francesca, Möller, Johannes S., Kohama, Yoshimitsu, Ghannadzadeh, Saman, Ardavan, Arzhang, Blundell, Stephen J., Lancaster, Tom, Xiao, Fan, Williams, Robert C., Pratt, Francis L., Baker, Peter J., Wierschem, Keola, Lapidus, Saul H., Stone, Kevin H., Stephens, Peter W., Bendix, Jesper, Woods, Toby J., Carreiro, Kimberly E., Tran, Hope E., Villa, Cecelia J., and Manson, Jamie L. Antiferromagnetism in a Family of S = 1 Square Lattice Coordination Polymers NiX 2 (pyz) 2 (X = Cl, Br, I, NCS; pyz = Pyrazine). United States: N. p., 2016. Web. doi:10.1021/acs.inorgchem.5b02991.
Liu, Junjie, Goddard, Paul A., Singleton, John, Brambleby, Jamie, Foronda, Francesca, Möller, Johannes S., Kohama, Yoshimitsu, Ghannadzadeh, Saman, Ardavan, Arzhang, Blundell, Stephen J., Lancaster, Tom, Xiao, Fan, Williams, Robert C., Pratt, Francis L., Baker, Peter J., Wierschem, Keola, Lapidus, Saul H., Stone, Kevin H., Stephens, Peter W., Bendix, Jesper, Woods, Toby J., Carreiro, Kimberly E., Tran, Hope E., Villa, Cecelia J., & Manson, Jamie L. Antiferromagnetism in a Family of S = 1 Square Lattice Coordination Polymers NiX 2 (pyz) 2 (X = Cl, Br, I, NCS; pyz = Pyrazine). United States. https://doi.org/10.1021/acs.inorgchem.5b02991
Liu, Junjie, Goddard, Paul A., Singleton, John, Brambleby, Jamie, Foronda, Francesca, Möller, Johannes S., Kohama, Yoshimitsu, Ghannadzadeh, Saman, Ardavan, Arzhang, Blundell, Stephen J., Lancaster, Tom, Xiao, Fan, Williams, Robert C., Pratt, Francis L., Baker, Peter J., Wierschem, Keola, Lapidus, Saul H., Stone, Kevin H., Stephens, Peter W., Bendix, Jesper, Woods, Toby J., Carreiro, Kimberly E., Tran, Hope E., Villa, Cecelia J., and Manson, Jamie L. Mon . "Antiferromagnetism in a Family of S = 1 Square Lattice Coordination Polymers NiX 2 (pyz) 2 (X = Cl, Br, I, NCS; pyz = Pyrazine)". United States. https://doi.org/10.1021/acs.inorgchem.5b02991.
@article{osti_1392921,
title = {Antiferromagnetism in a Family of S = 1 Square Lattice Coordination Polymers NiX 2 (pyz) 2 (X = Cl, Br, I, NCS; pyz = Pyrazine)},
author = {Liu, Junjie and Goddard, Paul A. and Singleton, John and Brambleby, Jamie and Foronda, Francesca and Möller, Johannes S. and Kohama, Yoshimitsu and Ghannadzadeh, Saman and Ardavan, Arzhang and Blundell, Stephen J. and Lancaster, Tom and Xiao, Fan and Williams, Robert C. and Pratt, Francis L. and Baker, Peter J. and Wierschem, Keola and Lapidus, Saul H. and Stone, Kevin H. and Stephens, Peter W. and Bendix, Jesper and Woods, Toby J. and Carreiro, Kimberly E. and Tran, Hope E. and Villa, Cecelia J. and Manson, Jamie L.},
abstractNote = {The crystal structures of NiX2(pyz)(2) (X = Cl (1), Br (2), I (3), and NCS (4)) were determined by synchrotron X-ray powder diffraction. All four compounds consist of two-dimensional (2D) square arrays self-assembled from octahedral NiN4X2 units that are bridged by pyz ligands. The 2D layered motifs displayed by 1-4 are relevant to bifluoride-bridged [Ni(HF2) (pyz)(2)]EF6 (E = P, Sb), which also possess the same 2D layers. In contrast, terminal X ligands occupy axial positions in 1-4 and cause a staggered packing of adjacent layers. Long-range antiferromagnetic (AFM) order occurs below 1.5 (Cl), 1.9 (Br and NCS), and 2.5 K (I) as determined by heat capacity and muon-spin relaxation. The single-ion anisotropy and g factor of 2, 3, and 4 were measured by electron-spin resonance with no evidence for zero field splitting (ZFS) being observed. The magnetism of 1-4 spans the spectrum from quasi-two-dimensional (2D) to three-dimensional (3D) antiferromagnetism. Nearly identical results and thermodynamic features were obtained for 2 and 4 as shown by pulsed-field magnetization, magnetic susceptibility, as well as their Neel temperatures. Magnetization curves for 2 and 4 calculated by quantum Monte Carlo simulation also show excellent agreement with the pulsed-field data. Compound 3 is characterized as a 3D AFM with the interlayer interaction (j(perpendicular to)) being slightly stronger than the intralayer interaction along Ni-pyz-Ni segments (j(pyz)) within the two-dimensional [Ni(pyz)(2)](2+) square planes. Regardless of X, j(pyz), is similar for the four compounds and is roughly 1 K.},
doi = {10.1021/acs.inorgchem.5b02991},
url = {https://www.osti.gov/biblio/1392921}, journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 7,
volume = 55,
place = {United States},
year = {2016},
month = {4}
}