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Title: Control of the third dimension in copper-based square-lattice antiferromagnets

Abstract

Using a mixed-ligand synthetic scheme, we create a family of quasi-two-dimensional antiferromagnets, namely, [Cu(HF2)(pyz)(2)]ClO4 [pyz = pyrazine], [CuL2(pyz)(2)](ClO4)(2) [L = pyO = pyridine-N-oxide and 4-phpy-O = 4-phenylpyridine-N-oxide. These materials are shown to possess equivalent two-dimensional [Cu(pyz)(2)](2+) nearly square layers, but exhibit interlayer spacings that vary from 6.5713 to 16.777 angstrom, as dictated by the axial ligands. We present the structural and magnetic properties of this family as determined via x-ray diffraction, electron-spin resonance, pulsed-and quasistatic-field magnetometry and muon-spin rotation, and compare them to those of the prototypical two-dimensional magnetic polymer Cu(pyz)(2)(ClO4)(2). We find that, within the limits of the experimental error, the two-dimensional, intralayer exchange coupling in our family of materials remains largely unaffected by the axial ligand substitution, while the observed magnetic ordering temperature (1.91 K for the material with the HF2 axial ligand, 1.70 K for the pyO and 1.63 K for the 4-phpy-O) decreases slowly with increasing layer separation. Despite the structural motifs common to this family and Cu(pyz)(2)(ClO4)(2), the latter has significantly stronger two-dimensional exchange interactions and hence a higher ordering temperature. We discuss these results, as well as the mechanisms that might drive the long-range order in these materials, in terms of departures from themore » ideal S = 1/2 two-dimensional square-lattice Heisenberg antiferromagnet. In particular, we find that both spin-exchange anisotropy in the intralayer interaction and interlayer couplings (exchange, dipolar, or both) are needed to account for the observed ordering temperatures, with the intralayer anisotropy becoming more important as the layers are pulled further apart.« less

Authors:
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Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1352679
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 93; Journal Issue: 9; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English

Citation Formats

Goddard, Paul A., Singleton, John, Franke, Isabel, Möller, Johannes S., Lancaster, Tom, Steele, Andrew J., Topping, Craig V., Blundell, Stephen J., Pratt, Francis L., Baines, C., Bendix, Jesper, McDonald, Ross D., Brambleby, Jamie, Lees, Martin R., Lapidus, Saul H., Stephens, Peter W., Twamley, Brendan W., Conner, Marianne M., Funk, Kylee, Corbey, Jordan F., Tran, Hope E., Schlueter, J. A., and Manson, Jamie L. Control of the third dimension in copper-based square-lattice antiferromagnets. United States: N. p., 2016. Web. doi:10.1103/PhysRevB.93.094430.
Goddard, Paul A., Singleton, John, Franke, Isabel, Möller, Johannes S., Lancaster, Tom, Steele, Andrew J., Topping, Craig V., Blundell, Stephen J., Pratt, Francis L., Baines, C., Bendix, Jesper, McDonald, Ross D., Brambleby, Jamie, Lees, Martin R., Lapidus, Saul H., Stephens, Peter W., Twamley, Brendan W., Conner, Marianne M., Funk, Kylee, Corbey, Jordan F., Tran, Hope E., Schlueter, J. A., & Manson, Jamie L. Control of the third dimension in copper-based square-lattice antiferromagnets. United States. https://doi.org/10.1103/PhysRevB.93.094430
Goddard, Paul A., Singleton, John, Franke, Isabel, Möller, Johannes S., Lancaster, Tom, Steele, Andrew J., Topping, Craig V., Blundell, Stephen J., Pratt, Francis L., Baines, C., Bendix, Jesper, McDonald, Ross D., Brambleby, Jamie, Lees, Martin R., Lapidus, Saul H., Stephens, Peter W., Twamley, Brendan W., Conner, Marianne M., Funk, Kylee, Corbey, Jordan F., Tran, Hope E., Schlueter, J. A., and Manson, Jamie L. 2016. "Control of the third dimension in copper-based square-lattice antiferromagnets". United States. https://doi.org/10.1103/PhysRevB.93.094430.
@article{osti_1352679,
title = {Control of the third dimension in copper-based square-lattice antiferromagnets},
author = {Goddard, Paul A. and Singleton, John and Franke, Isabel and Möller, Johannes S. and Lancaster, Tom and Steele, Andrew J. and Topping, Craig V. and Blundell, Stephen J. and Pratt, Francis L. and Baines, C. and Bendix, Jesper and McDonald, Ross D. and Brambleby, Jamie and Lees, Martin R. and Lapidus, Saul H. and Stephens, Peter W. and Twamley, Brendan W. and Conner, Marianne M. and Funk, Kylee and Corbey, Jordan F. and Tran, Hope E. and Schlueter, J. A. and Manson, Jamie L.},
abstractNote = {Using a mixed-ligand synthetic scheme, we create a family of quasi-two-dimensional antiferromagnets, namely, [Cu(HF2)(pyz)(2)]ClO4 [pyz = pyrazine], [CuL2(pyz)(2)](ClO4)(2) [L = pyO = pyridine-N-oxide and 4-phpy-O = 4-phenylpyridine-N-oxide. These materials are shown to possess equivalent two-dimensional [Cu(pyz)(2)](2+) nearly square layers, but exhibit interlayer spacings that vary from 6.5713 to 16.777 angstrom, as dictated by the axial ligands. We present the structural and magnetic properties of this family as determined via x-ray diffraction, electron-spin resonance, pulsed-and quasistatic-field magnetometry and muon-spin rotation, and compare them to those of the prototypical two-dimensional magnetic polymer Cu(pyz)(2)(ClO4)(2). We find that, within the limits of the experimental error, the two-dimensional, intralayer exchange coupling in our family of materials remains largely unaffected by the axial ligand substitution, while the observed magnetic ordering temperature (1.91 K for the material with the HF2 axial ligand, 1.70 K for the pyO and 1.63 K for the 4-phpy-O) decreases slowly with increasing layer separation. Despite the structural motifs common to this family and Cu(pyz)(2)(ClO4)(2), the latter has significantly stronger two-dimensional exchange interactions and hence a higher ordering temperature. We discuss these results, as well as the mechanisms that might drive the long-range order in these materials, in terms of departures from the ideal S = 1/2 two-dimensional square-lattice Heisenberg antiferromagnet. In particular, we find that both spin-exchange anisotropy in the intralayer interaction and interlayer couplings (exchange, dipolar, or both) are needed to account for the observed ordering temperatures, with the intralayer anisotropy becoming more important as the layers are pulled further apart.},
doi = {10.1103/PhysRevB.93.094430},
url = {https://www.osti.gov/biblio/1352679}, journal = {Physical Review B},
issn = {2469-9950},
number = 9,
volume = 93,
place = {United States},
year = {Tue Mar 01 00:00:00 EST 2016},
month = {Tue Mar 01 00:00:00 EST 2016}
}

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Works referencing / citing this record:

Magnetic order and enhanced exchange in the quasi-one-dimensional molecule-based antiferromagnet Cu(NO 3 ) 2 (pyz) 3
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Magnetic properties of a quasi-two-dimensional S = 1 2 Heisenberg antiferromagnet with distorted square lattice
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Interplay of Spin and Spatial Anisotropy in Low-Dimensional Quantum Magnets with Spin 1/2
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