Spin–Lattice Coupling Across the Magnetic Quantum-Phase Transition in Copper-Containing Coordination Polymers
Abstract
We measured the infrared vibrational properties of two copper-containing coordination polymers, [Cu(pyz)2(2-HOpy)2]-(PF6)2 and [Cu(pyz)1.5(4-HOpy)2](ClO4)2, under different external stimuli in order to explore the microscopic aspects of spin-lattice coupling. While the temperature and pressure control hydrogen bonding, an applied field drives these materials from the antiferromagnetic → fully saturated state. Analysis of the pyrazine (pyz)-related vibrational modes across the magnetic quantum-phase transition provides a superb local probe of magnetoelastic coupling because the pyz ligand functions as the primary exchange pathway and is present in both systems. Strikingly, the PF6- compound employs several pyz-related distortions in support of the magnetically driven transition, whereas the ClO4- system requires only a single out-of-plane pyz bending mode. Here, bringing these findings together with magnetoinfrared spectra from other copper complexes reveals spin-lattice coupling across the magnetic quantum-phase transition as a function of the structural and magnetic dimensionality. Coupling is maximized in [Cu(pyz)1.5(4-HOpy)2](ClO4)2 because of itas ladderlike character. Although spin-lattice interactions can also be explored under compression, differences in the local structure and dimensionality drive these materials to unique high-pressure phases. Symmetry analysis suggests that the high-pressure phase of the ClO4- compound may be ferroelectric.
- Authors:
-
[1];
[1];
[1];
[1];
[1];
[1]
- Univ. of Tennessee, Knoxville, TN (United States)
- Clark Univ., Worcester, MA (United States)
- The George Washington Univ., Washington, D.C. (United States)
- National High Magnetic Field Lab., Tallahassee, FL (United States)
- Publication Date:
- Research Org.:
- Univ. of Illinois at Chicago, IL (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA), Office of Defense Programs (DP); National Science Foundation (NSF)
- OSTI Identifier:
- 1778248
- Grant/Contract Number:
- NA0003975; AC98-06CH10886; DMR-1707846
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 59; Journal Issue: 4; 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; Ligands; Oscillation; Magnetic properties; Phase transitions; Materials
Citation Formats
Hughey, Kendall D., Harms, Nathan C., O’Neal, Kenneth R., Clune, Amanda J., Monroe, Jeffrey C., Blockmon, Avery L., Landee, Christopher P., Liu, Zhenxian, Ozerov, Mykhaylo, and Musfeldt, Janice L. Spin–Lattice Coupling Across the Magnetic Quantum-Phase Transition in Copper-Containing Coordination Polymers. United States: N. p., 2020.
Web. doi:10.1021/acs.inorgchem.9b02394.
Hughey, Kendall D., Harms, Nathan C., O’Neal, Kenneth R., Clune, Amanda J., Monroe, Jeffrey C., Blockmon, Avery L., Landee, Christopher P., Liu, Zhenxian, Ozerov, Mykhaylo, & Musfeldt, Janice L. Spin–Lattice Coupling Across the Magnetic Quantum-Phase Transition in Copper-Containing Coordination Polymers. United States. https://doi.org/10.1021/acs.inorgchem.9b02394
Hughey, Kendall D., Harms, Nathan C., O’Neal, Kenneth R., Clune, Amanda J., Monroe, Jeffrey C., Blockmon, Avery L., Landee, Christopher P., Liu, Zhenxian, Ozerov, Mykhaylo, and Musfeldt, Janice L. Mon .
"Spin–Lattice Coupling Across the Magnetic Quantum-Phase Transition in Copper-Containing Coordination Polymers". United States. https://doi.org/10.1021/acs.inorgchem.9b02394. https://www.osti.gov/servlets/purl/1778248.
@article{osti_1778248,
title = {Spin–Lattice Coupling Across the Magnetic Quantum-Phase Transition in Copper-Containing Coordination Polymers},
author = {Hughey, Kendall D. and Harms, Nathan C. and O’Neal, Kenneth R. and Clune, Amanda J. and Monroe, Jeffrey C. and Blockmon, Avery L. and Landee, Christopher P. and Liu, Zhenxian and Ozerov, Mykhaylo and Musfeldt, Janice L.},
abstractNote = {We measured the infrared vibrational properties of two copper-containing coordination polymers, [Cu(pyz)2(2-HOpy)2]-(PF6)2 and [Cu(pyz)1.5(4-HOpy)2](ClO4)2, under different external stimuli in order to explore the microscopic aspects of spin-lattice coupling. While the temperature and pressure control hydrogen bonding, an applied field drives these materials from the antiferromagnetic → fully saturated state. Analysis of the pyrazine (pyz)-related vibrational modes across the magnetic quantum-phase transition provides a superb local probe of magnetoelastic coupling because the pyz ligand functions as the primary exchange pathway and is present in both systems. Strikingly, the PF6- compound employs several pyz-related distortions in support of the magnetically driven transition, whereas the ClO4- system requires only a single out-of-plane pyz bending mode. Here, bringing these findings together with magnetoinfrared spectra from other copper complexes reveals spin-lattice coupling across the magnetic quantum-phase transition as a function of the structural and magnetic dimensionality. Coupling is maximized in [Cu(pyz)1.5(4-HOpy)2](ClO4)2 because of itas ladderlike character. Although spin-lattice interactions can also be explored under compression, differences in the local structure and dimensionality drive these materials to unique high-pressure phases. Symmetry analysis suggests that the high-pressure phase of the ClO4- compound may be ferroelectric.},
doi = {10.1021/acs.inorgchem.9b02394},
journal = {Inorganic Chemistry},
number = 4,
volume = 59,
place = {United States},
year = {Mon Feb 03 00:00:00 EST 2020},
month = {Mon Feb 03 00:00:00 EST 2020}
}
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