Developing the Pressure–Temperature–Magnetic Field Phase Diagram of Multiferroic [(CH3)2NH2]Mn(HCOO)3
Abstract
We combined Raman scattering and magnetic susceptibility to explore the properties of [(CH3)2NH2]Mn(HCOO)3 under compression. Analysis of the formate bending mode reveals a broad two-phase region surrounding the 4.2 GPa critical pressure that becomes increasingly sluggish below the order–disorder transition due to the extensive hydrogen-bonding network. Although the paraelectric and ferroelectric phases have different space groups at ambient-pressure conditions, they both drive toward P1 symmetry under compression. This is a direct consequence of how the order–disorder transition changes under pressure. We bring these findings together with prior magnetization work to create a pressure–temperature–magnetic field phase diagram, unveiling entanglement, competition, and a progression of symmetry-breaking effects that underlie functionality in this molecule-based multiferroic. Furthermore, that the high-pressure P1 phase is a subgroup of the ferroelectric Cc suggests the possibility of enhanced electric polarization as well as opportunity for strain control.
- Authors:
-
[1];
[1];
[1];
[1];
[3];
[1]
- Univ. of Tennessee, Knoxville, TN (United States)
- Central Michigan Univ., Mount Pleasant, MI (United States); New Jersey Institute of Technology, Newark, NJ (United States)
- Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
- Univ. of Illinois, Chicago, IL (United States)
- Publication Date:
- Research Org.:
- Univ. of Illinois, Chicago, IL (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA), Office of Defense Programs (DP)
- OSTI Identifier:
- 1767059
- Grant/Contract Number:
- NA0003975; AC98-06CH10886
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 59; Journal Issue: 14; 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; Group theory; Magnetic properties; Compression; Phase transitions; Polarization
Citation Formats
Clune, Amanda, Harms, Nathan, O’Neal, Kenneth R., Hughey, Kendall, Smith, Kevin A., Obeysekera, Dimuthu, Haddock, John, Dalal, Naresh S., Yang, Junjie, Liu, Zhenxian, and Musfeldt, Janice L. Developing the Pressure–Temperature–Magnetic Field Phase Diagram of Multiferroic [(CH3)2NH2]Mn(HCOO)3. United States: N. p., 2020.
Web. doi:10.1021/acs.inorgchem.0c01225.
Clune, Amanda, Harms, Nathan, O’Neal, Kenneth R., Hughey, Kendall, Smith, Kevin A., Obeysekera, Dimuthu, Haddock, John, Dalal, Naresh S., Yang, Junjie, Liu, Zhenxian, & Musfeldt, Janice L. Developing the Pressure–Temperature–Magnetic Field Phase Diagram of Multiferroic [(CH3)2NH2]Mn(HCOO)3. United States. https://doi.org/10.1021/acs.inorgchem.0c01225
Clune, Amanda, Harms, Nathan, O’Neal, Kenneth R., Hughey, Kendall, Smith, Kevin A., Obeysekera, Dimuthu, Haddock, John, Dalal, Naresh S., Yang, Junjie, Liu, Zhenxian, and Musfeldt, Janice L. Tue .
"Developing the Pressure–Temperature–Magnetic Field Phase Diagram of Multiferroic [(CH3)2NH2]Mn(HCOO)3". United States. https://doi.org/10.1021/acs.inorgchem.0c01225. https://www.osti.gov/servlets/purl/1767059.
@article{osti_1767059,
title = {Developing the Pressure–Temperature–Magnetic Field Phase Diagram of Multiferroic [(CH3)2NH2]Mn(HCOO)3},
author = {Clune, Amanda and Harms, Nathan and O’Neal, Kenneth R. and Hughey, Kendall and Smith, Kevin A. and Obeysekera, Dimuthu and Haddock, John and Dalal, Naresh S. and Yang, Junjie and Liu, Zhenxian and Musfeldt, Janice L.},
abstractNote = {We combined Raman scattering and magnetic susceptibility to explore the properties of [(CH3)2NH2]Mn(HCOO)3 under compression. Analysis of the formate bending mode reveals a broad two-phase region surrounding the 4.2 GPa critical pressure that becomes increasingly sluggish below the order–disorder transition due to the extensive hydrogen-bonding network. Although the paraelectric and ferroelectric phases have different space groups at ambient-pressure conditions, they both drive toward P1 symmetry under compression. This is a direct consequence of how the order–disorder transition changes under pressure. We bring these findings together with prior magnetization work to create a pressure–temperature–magnetic field phase diagram, unveiling entanglement, competition, and a progression of symmetry-breaking effects that underlie functionality in this molecule-based multiferroic. Furthermore, that the high-pressure P1 phase is a subgroup of the ferroelectric Cc suggests the possibility of enhanced electric polarization as well as opportunity for strain control.},
doi = {10.1021/acs.inorgchem.0c01225},
journal = {Inorganic Chemistry},
number = 14,
volume = 59,
place = {United States},
year = {Tue Jul 07 00:00:00 EDT 2020},
month = {Tue Jul 07 00:00:00 EDT 2020}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Controlling Magnetic Order and Quantum Disorder in Molecule-Based Magnets
journal, May 2014
- Lancaster, T.; Goddard, P. A.; Blundell, S. J.
- Physical Review Letters, Vol. 112, Issue 20
A diamond anvil cell for the investigation of superconductivity under pressures of up to 50 GPa: Pb as a low temperature manometer
journal, September 1988
- Bireckoven, B.; Wittig, J.
- Journal of Physics E: Scientific Instruments, Vol. 21, Issue 9
Conformational and phase transformations of chlorocyclohexane at high pressures by Raman spectroscopy
journal, February 2008
- Dong, Zhaohui; Beilby, Nicholas G.; Huang, Yining
- The Journal of Chemical Physics, Vol. 128, Issue 7
Structural Tuning of Energetic Material Bis(1 H -tetrazol-5-yl)amine Monohydrate under Pressures Probed by Vibrational Spectroscopy and X-ray Diffraction
journal, November 2014
- Zhou, Liang; Shinde, Nilesh; Hu, Anguang
- The Journal of Physical Chemistry C, Vol. 118, Issue 46
Designing new ferroelectrics with a general strategy
journal, January 2017
- Xu, Ke; Lu, Xue-Zeng; Xiang, Hongjun
- npj Quantum Materials, Vol. 2, Issue 1
Optical pressure sensors for high-pressure–high-temperature studies in a diamond anvil cell
journal, December 2007
- Datchi, F.; Dewaele, A.; Loubeyre, P.
- High Pressure Research, Vol. 27, Issue 4
Magnetic field-temperature phase diagram of multiferroic
journal, September 2017
- Clune, A. J.; Hughey, K. D.; Lee, C.
- Physical Review B, Vol. 96, Issue 10
Multiferroics of spin origin
journal, July 2014
- Tokura, Yoshinori; Seki, Shinichiro; Nagaosa, Naoto
- Reports on Progress in Physics, Vol. 77, Issue 7
Magnetic field-temperature phase diagram of multiferroic (NH4)2FeCl5·H2O
journal, August 2019
- Clune, Amanda J.; Nam, Jisoo; Lee, Minseong
- npj Quantum Materials, Vol. 4, Issue 1
Pressure-Induced Polymorphic, Optical, and Electronic Transitions of Formamidinium Lead Iodide Perovskite
journal, April 2017
- Wang, Pan; Guan, Jiwen; Galeschuk, Draven T. K.
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 10
Above-Room-Temperature Magnetodielectric Coupling in a Possible Molecule-Based Multiferroic: Triethylmethylammonium Tetrabromoferrate(III)
journal, November 2012
- Cai, Hong-Ling; Zhang, Yi; Fu, Da-Wei
- Journal of the American Chemical Society, Vol. 134, Issue 45
Commensurate magnetic structures of determined by single-crystal neutron diffraction
journal, April 2008
- Vecchini, C.; Chapon, L. C.; Brown, P. J.
- Physical Review B, Vol. 77, Issue 13
Why Are There so Few Magnetic Ferroelectrics?
journal, July 2000
- Hill, Nicola A.
- The Journal of Physical Chemistry B, Vol. 104, Issue 29
There's Room in the Middle
journal, October 2007
- Cheetham, A. K.; Rao, C. N. R.
- Science, Vol. 318, Issue 5847
Locking of Methylammonium by Pressure-Enhanced H-Bonding in (CH 3 NH 3 )PbBr 3 Hybrid Perovskite
journal, December 2017
- Capitani, F.; Marini, C.; Caramazza, S.
- The Journal of Physical Chemistry C, Vol. 121, Issue 50
The effect of pressure on the magnetic properties of the molecule-based canted metamagnet decamethylferrocenium 2,3-dicyano-1,4-naphthoquinonide, FeCp* 2 [DCNQ]
journal, July 2003
- Hamlin, James J.; Beckett, Brett R.; Tomita, Takahiro
- Polyhedron, Vol. 22, Issue 14-17
Thermodynamic properties of the new multiferroic material (NH 4 ) 2 [FeCl 5 (H 2 O)]
journal, December 2013
- Ackermann, M.; Brüning, D.; Lorenz, T.
- New Journal of Physics, Vol. 15, Issue 12
Characterization of the Order−Disorder Dielectric Transition in the Hybrid Organic−Inorganic Perovskite-Like Formate Mn(HCOO) 3 [(CH 3 ) 2 NH 2 ]
journal, February 2010
- Sánchez-Andújar, M.; Presedo, S.; Yáñez-Vilar, S.
- Inorganic Chemistry, Vol. 49, Issue 4
Specific volume measurements of Cu, Mo, Pd, and Ag and calibration of the ruby R 1 fluorescence pressure gauge from 0.06 to 1 Mbar
journal, June 1978
- Mao, H. K.; Bell, P. M.; Shaner, J. W.
- Journal of Applied Physics, Vol. 49, Issue 6
The Role of Order–Disorder Transitions in the Quest for Molecular Multiferroics: Structural and Magnetic Neutron Studies of a Mixed Valence Iron(II)–Iron(III) Formate Framework
journal, November 2012
- Cañadillas-Delgado, Laura; Fabelo, Oscar; Rodríguez-Velamazán, J. Alberto
- Journal of the American Chemical Society, Vol. 134, Issue 48
Multiferroicity in an organic charge-transfer salt that is suggestive of electric-dipole-driven magnetism
journal, August 2012
- Lunkenheimer, Peter; Müller, Jens; Krohns, Stephan
- Nature Materials, Vol. 11, Issue 9
Electric Control of Magnetization and Interplay between Orbital Ordering and Ferroelectricity in a Multiferroic Metal-Organic Framework
journal, May 2011
- Stroppa, Alessandro; Jain, Prashant; Barone, Paolo
- Angewandte Chemie International Edition, Vol. 50, Issue 26
Growth of centimeter-sized [(CH 3 ) 2 NH 2 ][Mn(HCOO) 3 ] hybrid formate perovskite single crystals and Raman evidence of pressure-induced phase transitions
journal, January 2017
- Xin, Lipeng; Fan, Zhen; Li, Guanghui
- New Journal of Chemistry, Vol. 41, Issue 1
Phonon mode links ferroicities in multiferroic
journal, November 2017
- Hughey, Kendall D.; Clune, Amanda J.; Yokosuk, Michael O.
- Physical Review B, Vol. 96, Issue 18
Giant spin-driven ferroelectric polarization in TbMnO3 under high pressure
journal, September 2014
- Aoyama, T.; Yamauchi, K.; Iyama, A.
- Nature Communications, Vol. 5, Issue 1
Multiferroic Behavior Associated with an Order−Disorder Hydrogen Bonding Transition in Metal−Organic Frameworks (MOFs) with the Perovskite ABX 3 Architecture
journal, September 2009
- Jain, Prashant; Ramachandran, Vasanth; Clark, Ronald J.
- Journal of the American Chemical Society, Vol. 131, Issue 38
Multiferroic Materials Based on Organic Transition-Metal Molecular Nanowires
journal, August 2012
- Wu, Menghao; Burton, J. D.; Tsymbal, Evgeny Y.
- Journal of the American Chemical Society, Vol. 134, Issue 35
Pressure-induced structural transition in copper pyrazine dinitrate and implications for quantum magnetism
journal, March 2016
- O'Neal, K. R.; Zhou, J.; Cherian, J. G.
- Physical Review B, Vol. 93, Issue 10
Order–Disorder Transition and Weak Ferromagnetism in the Perovskite Metal Formate Frameworks of [(CH 3 ) 2 NH 2 ][M(HCOO) 3 ] and [(CH 3 ) 2 ND 2 ][M(HCOO) 3 ] (M = Ni, Mn)
journal, December 2013
- Mączka, Mirosław; Gągor, Anna; Macalik, Bogusław
- Inorganic Chemistry, Vol. 53, Issue 1
Magnetic Ordering-Induced Multiferroic Behavior in [CH 3 NH 3 ][Co(HCOO) 3 ] Metal–Organic Framework
journal, January 2016
- Gómez-Aguirre, L. Claudia; Pato-Doldán, Breogán; Mira, J.
- Journal of the American Chemical Society, Vol. 138, Issue 4
Pressure-induced enhancement of the transition temperature of a genuine organic weak-ferromagnet up to 65 K
journal, May 2001
- Mito, M.; Kawae, T.; Takeda, K.
- Polyhedron, Vol. 20, Issue 11-14
Disorder-order phase transition at high pressure in ammonium fluoride
journal, September 2017
- Bellin, Christophe; Mafety, Adrien; Narayana, Chandrabhas
- Physical Review B, Vol. 96, Issue 9
Thin films of coordination polymer magnets
journal, January 2011
- Talham, Daniel R.; Meisel, Mark W.
- Chemical Society Reviews, Vol. 40, Issue 6
Structure–Property Relations in Multiferroic [(CH 3 ) 2 NH 2 ] M (HCOO) 3 ( M = Mn, Co, Ni)
journal, August 2018
- Hughey, Kendall D.; Clune, Amanda J.; Yokosuk, Michael O.
- Inorganic Chemistry, Vol. 57, Issue 18
Magnetoelectric coupling in the paramagnetic state of a metal-organic framework
journal, June 2013
- Wang, W.; Yan, L. -Q.; Cong, J. -Z.
- Scientific Reports, Vol. 3, Issue 1
Cross coupling between electric and magnetic orders in a multiferroic metal-organic framework
journal, August 2014
- Tian, Ying; Stroppa, Alessandro; Chai, Yisheng
- Scientific Reports, Vol. 4, Issue 1
Bilbao Crystallographic Server: I. Databases and crystallographic computing programs
journal, January 2006
- Aroyo, Mois Ilia; Perez-Mato, Juan Manuel; Capillas, Cesar
- Zeitschrift für Kristallographie - Crystalline Materials, Vol. 221, Issue 1
Bilbao Crystallographic Server. II. Representations of crystallographic point groups and space groups
journal, March 2006
- Aroyo, Mois I.; Kirov, Asen; Capillas, Cesar
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 62, Issue 2
Adiabatic physics of an exchange-coupled spin-dimer system: Magnetocaloric effect, zero-point fluctuations, and possible two-dimensional universal behavior
journal, January 2017
- Brambleby, J.; Goddard, P. A.; Singleton, J.
- Physical Review B, Vol. 95, Issue 2
Molecular magnetism: from chemical design to spin control in molecules, materials and devices
journal, October 2019
- Coronado, Eugenio
- Nature Reviews Materials
Classifying multiferroics: Mechanisms and effects
journal, March 2009
- Khomskii, Daniel
- Physics, Vol. 2
Emerging routes to multiferroics
journal, October 2009
- Ramesh, Ramamoorthy
- Nature, Vol. 461, Issue 7268
Multiferroics by Rational Design: Implementing Ferroelectricity in Molecule-Based Magnets
journal, July 2012
- Pardo, Emilio; Train, Cyrille; Liu, Hongbo
- Angewandte Chemie International Edition, Vol. 51, Issue 33
Multiferroics: a magnetic twist for ferroelectricity
journal, January 2007
- Cheong, Sang-Wook; Mostovoy, Maxim
- Nature Materials, Vol. 6, Issue 1
Pressure-induced enhancement of the magnetic anisotropy in
journal, January 2015
- Quintero, P. A.; Rajan, D.; Peprah, M. K.
- Physical Review B, Vol. 91, Issue 1
Molecular analog of multiferroics: Electric and magnetic field effects in many-electron mixed-valence dimers
journal, July 2012
- Bosch-Serrano, Cristian; Clemente-Juan, Juan M.; Coronado, Eugenio
- Physical Review B, Vol. 86, Issue 2
Perovskite-like Metal Formates with Weak Ferromagnetism and as Precursors to Amorphous Materials
journal, July 2004
- Wang, Xin-Yi; Gan, Lin; Zhang, Shi-Wei
- Inorganic Chemistry, Vol. 43, Issue 15
Ferroelectric space groups
journal, January 1986
- Litvin, D. B.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 42, Issue 1
Competing magnetostructural phases in a semiclassical system
journal, November 2017
- O’Neal, Kenneth R.; Lee, Jun Hee; Kim, Maeng-Suk
- npj Quantum Materials, Vol. 2, Issue 1
Switchable electric polarization and ferroelectric domains in a metal-organic-framework
journal, September 2016
- Jain, Prashant; Stroppa, Alessandro; Nabok, Dmitrii
- npj Quantum Materials, Vol. 1, Issue 1