Developing the Pressure–Temperature–Magnetic Field Phase Diagram of Multiferroic [(CH3)2NH2]Mn(HCOO)3

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.

doi:10.1021/acs.inorgchem.0c01225

Title: Developing the Pressure–Temperature–Magnetic Field Phase Diagram of Multiferroic [(CH₃)₂NH₂]Mn(HCOO)₃

Journal Article · Tue Jul 07 00:00:00 EDT 2020 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.0c01225· OSTI ID:1767059

^[1];

^[1]; Smith, Kevin A. ^[1]; Obeysekera, Dimuthu ^[2]; Haddock, John ^[3];

^[3]; Yang, Junjie ^[2]; Liu, Zhenxian ^[4];

^[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)

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Univ. of Illinois, Chicago, IL (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA), Office of Defense Programs (DP)

Grant/Contract Number:: NA0003975; AC98-06CH10886

OSTI ID:: 1767059

Journal Information:: Inorganic Chemistry, Vol. 59, Issue 14; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (50)

Controlling Magnetic Order and Quantum Disorder in Molecule-Based Magnets Lancaster, T.; Goddard, P. A.; Blundell, S. J. Physical Review Letters, Vol. 112, Issue 20 https://doi.org/10.1103/PhysRevLett.112.207201	journal	May 2014
A diamond anvil cell for the investigation of superconductivity under pressures of up to 50 GPa: Pb as a low temperature manometer Bireckoven, B.; Wittig, J. Journal of Physics E: Scientific Instruments, Vol. 21, Issue 9 https://doi.org/10.1088/0022-3735/21/9/004	journal	September 1988
Conformational and phase transformations of chlorocyclohexane at high pressures by Raman spectroscopy Dong, Zhaohui; Beilby, Nicholas G.; Huang, Yining The Journal of Chemical Physics, Vol. 128, Issue 7 https://doi.org/10.1063/1.2829408	journal	February 2008
Structural Tuning of Energetic Material Bis(1 H -tetrazol-5-yl)amine Monohydrate under Pressures Probed by Vibrational Spectroscopy and X-ray Diffraction Zhou, Liang; Shinde, Nilesh; Hu, Anguang The Journal of Physical Chemistry C, Vol. 118, Issue 46 https://doi.org/10.1021/jp507291m	journal	November 2014
Designing new ferroelectrics with a general strategy Xu, Ke; Lu, Xue-Zeng; Xiang, Hongjun npj Quantum Materials, Vol. 2, Issue 1 https://doi.org/10.1038/s41535-016-0001-8	journal	January 2017
Optical pressure sensors for high-pressure–high-temperature studies in a diamond anvil cell Datchi, F.; Dewaele, A.; Loubeyre, P. High Pressure Research, Vol. 27, Issue 4 https://doi.org/10.1080/08957950701659593	journal	December 2007
Magnetic field-temperature phase diagram of multiferroic $[{({CH}_{3})}_{2} {NH}_{2}] Mn {(HCOO)}_{3}$ Clune, A. J.; Hughey, K. D.; Lee, C. Physical Review B, Vol. 96, Issue 10 https://doi.org/10.1103/PhysRevB.96.104424	journal	September 2017
Multiferroics of spin origin Tokura, Yoshinori; Seki, Shinichiro; Nagaosa, Naoto Reports on Progress in Physics, Vol. 77, Issue 7 https://doi.org/10.1088/0034-4885/77/7/076501	journal	July 2014
Magnetic field-temperature phase diagram of multiferroic (NH4)2FeCl5·H2O Clune, Amanda J.; Nam, Jisoo; Lee, Minseong npj Quantum Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s41535-019-0180-1	journal	August 2019
Pressure-Induced Polymorphic, Optical, and Electronic Transitions of Formamidinium Lead Iodide Perovskite Wang, Pan; Guan, Jiwen; Galeschuk, Draven T. K. The Journal of Physical Chemistry Letters, Vol. 8, Issue 10 https://doi.org/10.1021/acs.jpclett.7b00665	journal	April 2017
Above-Room-Temperature Magnetodielectric Coupling in a Possible Molecule-Based Multiferroic: Triethylmethylammonium Tetrabromoferrate(III) Cai, Hong-Ling; Zhang, Yi; Fu, Da-Wei Journal of the American Chemical Society, Vol. 134, Issue 45 https://doi.org/10.1021/ja3073319	journal	November 2012
Commensurate magnetic structures of $R {Mn}_{2} O_{5}$ $(R = Y, Ho, Bi)$ determined by single-crystal neutron diffraction Vecchini, C.; Chapon, L. C.; Brown, P. J. Physical Review B, Vol. 77, Issue 13 https://doi.org/10.1103/PhysRevB.77.134434	journal	April 2008
Why Are There so Few Magnetic Ferroelectrics? Hill, Nicola A. The Journal of Physical Chemistry B, Vol. 104, Issue 29 https://doi.org/10.1021/jp000114x	journal	July 2000
There's Room in the Middle Cheetham, A. K.; Rao, C. N. R. Science, Vol. 318, Issue 5847 https://doi.org/10.1126/science.1147231	journal	October 2007
Locking of Methylammonium by Pressure-Enhanced H-Bonding in (CH ₃ NH ₃ )PbBr ₃ Hybrid Perovskite Capitani, F.; Marini, C.; Caramazza, S. The Journal of Physical Chemistry C, Vol. 121, Issue 50 https://doi.org/10.1021/acs.jpcc.7b11461	journal	December 2017
The effect of pressure on the magnetic properties of the molecule-based canted metamagnet decamethylferrocenium 2,3-dicyano-1,4-naphthoquinonide, FeCp* 2 [DCNQ] Hamlin, James J.; Beckett, Brett R.; Tomita, Takahiro Polyhedron, Vol. 22, Issue 14-17 https://doi.org/10.1016/S0277-5387(03)00179-7	journal	July 2003
Thermodynamic properties of the new multiferroic material (NH ₄ ) ₂ [FeCl ₅ (H ₂ O)] Ackermann, M.; Brüning, D.; Lorenz, T. New Journal of Physics, Vol. 15, Issue 12 https://doi.org/10.1088/1367-2630/15/12/123001	journal	December 2013
Characterization of the Order−Disorder Dielectric Transition in the Hybrid Organic−Inorganic Perovskite-Like Formate Mn(HCOO) ₃ [(CH ₃ ) ₂ NH ₂ ] Sánchez-Andújar, M.; Presedo, S.; Yáñez-Vilar, S. Inorganic Chemistry, Vol. 49, Issue 4 https://doi.org/10.1021/ic901872g	journal	February 2010
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 Mao, H. K.; Bell, P. M.; Shaner, J. W. Journal of Applied Physics, Vol. 49, Issue 6 https://doi.org/10.1063/1.325277	journal	June 1978
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 Cañadillas-Delgado, Laura; Fabelo, Oscar; Rodríguez-Velamazán, J. Alberto Journal of the American Chemical Society, Vol. 134, Issue 48 https://doi.org/10.1021/ja3082457	journal	November 2012
Multiferroicity in an organic charge-transfer salt that is suggestive of electric-dipole-driven magnetism Lunkenheimer, Peter; Müller, Jens; Krohns, Stephan Nature Materials, Vol. 11, Issue 9 https://doi.org/10.1038/nmat3400	journal	August 2012
Electric Control of Magnetization and Interplay between Orbital Ordering and Ferroelectricity in a Multiferroic Metal-Organic Framework Stroppa, Alessandro; Jain, Prashant; Barone, Paolo Angewandte Chemie International Edition, Vol. 50, Issue 26 https://doi.org/10.1002/anie.201101405	journal	May 2011
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 Xin, Lipeng; Fan, Zhen; Li, Guanghui New Journal of Chemistry, Vol. 41, Issue 1 https://doi.org/10.1039/C6NJ02798A	journal	January 2017
Phonon mode links ferroicities in multiferroic $[{({CH}_{3})}_{2} {NH}_{2}] {Mn (HCOO)}_{3}$ Hughey, Kendall D.; Clune, Amanda J.; Yokosuk, Michael O. Physical Review B, Vol. 96, Issue 18 https://doi.org/10.1103/PhysRevB.96.180305	journal	November 2017
Giant spin-driven ferroelectric polarization in TbMnO3 under high pressure Aoyama, T.; Yamauchi, K.; Iyama, A. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5927	journal	September 2014
Multiferroic Behavior Associated with an Order−Disorder Hydrogen Bonding Transition in Metal−Organic Frameworks (MOFs) with the Perovskite ABX ₃ Architecture Jain, Prashant; Ramachandran, Vasanth; Clark, Ronald J. Journal of the American Chemical Society, Vol. 131, Issue 38 https://doi.org/10.1021/ja904156s	journal	September 2009
Multiferroic Materials Based on Organic Transition-Metal Molecular Nanowires Wu, Menghao; Burton, J. D.; Tsymbal, Evgeny Y. Journal of the American Chemical Society, Vol. 134, Issue 35 https://doi.org/10.1021/ja304199x	journal	August 2012
Pressure-induced structural transition in copper pyrazine dinitrate and implications for quantum magnetism O'Neal, K. R.; Zhou, J.; Cherian, J. G. Physical Review B, Vol. 93, Issue 10 https://doi.org/10.1103/PhysRevB.93.104409	journal	March 2016
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) Mączka, Mirosław; Gągor, Anna; Macalik, Bogusław Inorganic Chemistry, Vol. 53, Issue 1 https://doi.org/10.1021/ic402425n	journal	December 2013
Magnetic Ordering-Induced Multiferroic Behavior in [CH ₃ NH ₃ ][Co(HCOO) ₃ ] Metal–Organic Framework Gómez-Aguirre, L. Claudia; Pato-Doldán, Breogán; Mira, J. Journal of the American Chemical Society, Vol. 138, Issue 4 https://doi.org/10.1021/jacs.5b11688	journal	January 2016
Pressure-induced enhancement of the transition temperature of a genuine organic weak-ferromagnet up to 65 K Mito, M.; Kawae, T.; Takeda, K. Polyhedron, Vol. 20, Issue 11-14 https://doi.org/10.1016/S0277-5387(01)00644-1	journal	May 2001
Disorder-order phase transition at high pressure in ammonium fluoride Bellin, Christophe; Mafety, Adrien; Narayana, Chandrabhas Physical Review B, Vol. 96, Issue 9 https://doi.org/10.1103/PhysRevB.96.094110	journal	September 2017
Thin films of coordination polymer magnets Talham, Daniel R.; Meisel, Mark W. Chemical Society Reviews, Vol. 40, Issue 6 https://doi.org/10.1039/c1cs15015d	journal	January 2011
Structure–Property Relations in Multiferroic [(CH ₃ ) ₂ NH ₂ ] M (HCOO) ₃ ( M = Mn, Co, Ni) Hughey, Kendall D.; Clune, Amanda J.; Yokosuk, Michael O. Inorganic Chemistry, Vol. 57, Issue 18 https://doi.org/10.1021/acs.inorgchem.8b01609	journal	August 2018
Magnetoelectric coupling in the paramagnetic state of a metal-organic framework Wang, W.; Yan, L. -Q.; Cong, J. -Z. Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02024	journal	June 2013
Cross coupling between electric and magnetic orders in a multiferroic metal-organic framework Tian, Ying; Stroppa, Alessandro; Chai, Yisheng Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep06062	journal	August 2014
Bilbao Crystallographic Server: I. Databases and crystallographic computing programs Aroyo, Mois Ilia; Perez-Mato, Juan Manuel; Capillas, Cesar Zeitschrift für Kristallographie - Crystalline Materials, Vol. 221, Issue 1 https://doi.org/10.1524/zkri.2006.221.1.15	journal	January 2006
Bilbao Crystallographic Server. II. Representations of crystallographic point groups and space groups Aroyo, Mois I.; Kirov, Asen; Capillas, Cesar Acta Crystallographica Section A Foundations of Crystallography, Vol. 62, Issue 2 https://doi.org/10.1107/S0108767305040286	journal	March 2006
Adiabatic physics of an exchange-coupled spin-dimer system: Magnetocaloric effect, zero-point fluctuations, and possible two-dimensional universal behavior Brambleby, J.; Goddard, P. A.; Singleton, J. Physical Review B, Vol. 95, Issue 2 https://doi.org/10.1103/PhysRevB.95.024404	journal	January 2017
Molecular magnetism: from chemical design to spin control in molecules, materials and devices Coronado, Eugenio Nature Reviews Materials https://doi.org/10.1038/s41578-019-0146-8	journal	October 2019
Classifying multiferroics: Mechanisms and effects Khomskii, Daniel Physics, Vol. 2 https://doi.org/10.1103/Physics.2.20	journal	March 2009
Emerging routes to multiferroics Ramesh, Ramamoorthy Nature, Vol. 461, Issue 7268 https://doi.org/10.1038/4611218a	journal	October 2009
Multiferroics by Rational Design: Implementing Ferroelectricity in Molecule-Based Magnets Pardo, Emilio; Train, Cyrille; Liu, Hongbo Angewandte Chemie International Edition, Vol. 51, Issue 33 https://doi.org/10.1002/anie.201202848	journal	July 2012
Multiferroics: a magnetic twist for ferroelectricity Cheong, Sang-Wook; Mostovoy, Maxim Nature Materials, Vol. 6, Issue 1 https://doi.org/10.1038/nmat1804	journal	January 2007
Pressure-induced enhancement of the magnetic anisotropy in $Mn {(N {(CN)}_{2})}_{2}$ Quintero, P. A.; Rajan, D.; Peprah, M. K. Physical Review B, Vol. 91, Issue 1 https://doi.org/10.1103/PhysRevB.91.014439	journal	January 2015
Molecular analog of multiferroics: Electric and magnetic field effects in many-electron mixed-valence dimers Bosch-Serrano, Cristian; Clemente-Juan, Juan M.; Coronado, Eugenio Physical Review B, Vol. 86, Issue 2 https://doi.org/10.1103/PhysRevB.86.024432	journal	July 2012
Perovskite-like Metal Formates with Weak Ferromagnetism and as Precursors to Amorphous Materials Wang, Xin-Yi; Gan, Lin; Zhang, Shi-Wei Inorganic Chemistry, Vol. 43, Issue 15 https://doi.org/10.1021/ic0498081	journal	July 2004
Ferroelectric space groups Litvin, D. B. Acta Crystallographica Section A Foundations of Crystallography, Vol. 42, Issue 1 https://doi.org/10.1107/S0108767386099920	journal	January 1986
Competing magnetostructural phases in a semiclassical system O’Neal, Kenneth R.; Lee, Jun Hee; Kim, Maeng-Suk npj Quantum Materials, Vol. 2, Issue 1 https://doi.org/10.1038/s41535-017-0065-0	journal	November 2017
Switchable electric polarization and ferroelectric domains in a metal-organic-framework Jain, Prashant; Stroppa, Alessandro; Nabok, Dmitrii npj Quantum Materials, Vol. 1, Issue 1 https://doi.org/10.1038/npjquantmats.2016.12	journal	September 2016

Similar Records

Structure–Property Relations in Multiferroic [(CH₃)₂NH₂]M(HCOO)₃ (M = Mn, Co, Ni)

Journal Article · Fri Aug 24 00:00:00 EDT 2018 · Inorganic Chemistry · OSTI ID:1767059

Hughey, Kendall D.; Clune, Amanda J.; Yokosuk, Michael O.; +8 more

Phonon mode links ferroicities in multiferroic

[{({CH}_{3})}_{2} {NH}_{2}] {Mn (HCOO)}_{3}

Journal Article · Wed Nov 22 00:00:00 EST 2017 · Physical Review B · OSTI ID:1767059

Hughey, Kendall D.; Clune, Amanda J.; Yokosuk, Michael O.; +9 more

Structural, magnetic and phonon properties of Cr(III)-doped perovskite metal formate framework [(CH{sub 3}){sub 2}NH{sub 2}][Mn(HCOO){sub 3}]

Journal Article · Sun May 15 00:00:00 EDT 2016 · Journal of Solid State Chemistry · OSTI ID:1767059

Mączka, Mirosław; Gągor, Anna; Hermanowicz, Krzysztof; +3 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Group theory
Magnetic properties
Compression
Phase transitions
Polarization

Title: Developing the Pressure–Temperature–Magnetic Field Phase Diagram of Multiferroic [(CH3)2NH2]Mn(HCOO)3

Citation Formats

References (50)

Similar Records

Related Subjects

Title: Developing the Pressure–Temperature–Magnetic Field Phase Diagram of Multiferroic [(CH₃)₂NH₂]Mn(HCOO)₃