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Title: Structure–Property Relations in Multiferroic [(CH 3) 2NH 2]M(HCOO) 3 (M = Mn, Co, Ni)

Abstract

In this paper, we bring together magnetization, infrared spectroscopy, and lattice dynamics calculations to uncover the magnetic field-temperature (B-T) phase diagrams and vibrational properties of the [(CH 3) 2NH 2]M(HCOO) 3 (M = Mn 2+, Co 2+, Ni 2+) family of multiferroics. While the magnetically driven transition to the fully saturated state in [(CH 3) 2NH 2]Mn(HCOO) 3 takes place at 15.3 T, substitution with Ni or Co drives the critical fields up toward 100 T, an unexpectedly high energy scale for these compounds. Analysis of the infrared spectrum of the Mn and Ni compounds across T C reveals doublet splitting of the formate bending mode which functions as an order parameter of the ferroelectric transition. By contrast, [(CH 3) 2NH 2]Co(HCOO) 3 reveals a surprising framework rigidity across the order-disorder transition due to modest distortions around the Co 2+ centers. The transition to the ferroelectric state is thus driven by the dimethylammonium cation freezing and the resulting hydrogen bonding. Under applied field, the Mn (and most likely, the Ni) compounds engage the formate bending mode to facilitate the transition to their fully saturated magnetic states, whereas the Co complex adopts a different mechanism involving formate stretching distortions to lowermore » the overall magnetic energy. Finally, similar structure–property relations involving substitution of transition-metal centers and control of the flexible molecular architecture are likely to exist in other molecule-based multiferroics.« less

Authors:
 [1];  [1];  [1];  [2];  [3];  [4]; ORCiD logo [3];  [2];  [5];  [4]; ORCiD logo [6]
  1. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  2. Fudan Univ., Shanghai (China). Key Lab. of Computational Physical Sciences. State Key Lab. of Surface Physics. Dept. of Physics; Collaborative Innovation Center of Advanced Microstructures, Nanjing (China)
  3. Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab). Dept. of Chemistry and Biochemistry
  4. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  5. Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
  6. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry. Dept. of Physics
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); LANL Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF); National Natural Science Foundation of China (NNSFC); Special Funds for Major State Basic Research (China); Qing Nian Ba Jian Program (China); Fok Ying Tung Education Foundation (China)
OSTI Identifier:
1467345
Report Number(s):
LA-UR-18-25204
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
AC52-06NA25396; DMR-1707846; DMR-1644779; 11374056; 2015CB921700
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 18; 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; High Magnetic Field Science

Citation Formats

Hughey, Kendall D., Clune, Amanda J., Yokosuk, Michael O., Li, Jing, Abhyankar, Nandita, Ding, Xiaxin, Dalal, Naresh S., Xiang, Hongjun, Smirnov, Dmitry, Singleton, John, and Musfeldt, Janice L. Structure–Property Relations in Multiferroic [(CH3)2NH2]M(HCOO)3 (M = Mn, Co, Ni). United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b01609.
Hughey, Kendall D., Clune, Amanda J., Yokosuk, Michael O., Li, Jing, Abhyankar, Nandita, Ding, Xiaxin, Dalal, Naresh S., Xiang, Hongjun, Smirnov, Dmitry, Singleton, John, & Musfeldt, Janice L. Structure–Property Relations in Multiferroic [(CH3)2NH2]M(HCOO)3 (M = Mn, Co, Ni). United States. https://doi.org/10.1021/acs.inorgchem.8b01609
Hughey, Kendall D., Clune, Amanda J., Yokosuk, Michael O., Li, Jing, Abhyankar, Nandita, Ding, Xiaxin, Dalal, Naresh S., Xiang, Hongjun, Smirnov, Dmitry, Singleton, John, and Musfeldt, Janice L. Fri . "Structure–Property Relations in Multiferroic [(CH3)2NH2]M(HCOO)3 (M = Mn, Co, Ni)". United States. https://doi.org/10.1021/acs.inorgchem.8b01609. https://www.osti.gov/servlets/purl/1467345.
@article{osti_1467345,
title = {Structure–Property Relations in Multiferroic [(CH3)2NH2]M(HCOO)3 (M = Mn, Co, Ni)},
author = {Hughey, Kendall D. and Clune, Amanda J. and Yokosuk, Michael O. and Li, Jing and Abhyankar, Nandita and Ding, Xiaxin and Dalal, Naresh S. and Xiang, Hongjun and Smirnov, Dmitry and Singleton, John and Musfeldt, Janice L.},
abstractNote = {In this paper, we bring together magnetization, infrared spectroscopy, and lattice dynamics calculations to uncover the magnetic field-temperature (B-T) phase diagrams and vibrational properties of the [(CH3)2NH2]M(HCOO)3 (M = Mn2+, Co2+, Ni2+) family of multiferroics. While the magnetically driven transition to the fully saturated state in [(CH3)2NH2]Mn(HCOO)3 takes place at 15.3 T, substitution with Ni or Co drives the critical fields up toward 100 T, an unexpectedly high energy scale for these compounds. Analysis of the infrared spectrum of the Mn and Ni compounds across TC reveals doublet splitting of the formate bending mode which functions as an order parameter of the ferroelectric transition. By contrast, [(CH3)2NH2]Co(HCOO)3 reveals a surprising framework rigidity across the order-disorder transition due to modest distortions around the Co2+ centers. The transition to the ferroelectric state is thus driven by the dimethylammonium cation freezing and the resulting hydrogen bonding. Under applied field, the Mn (and most likely, the Ni) compounds engage the formate bending mode to facilitate the transition to their fully saturated magnetic states, whereas the Co complex adopts a different mechanism involving formate stretching distortions to lower the overall magnetic energy. Finally, similar structure–property relations involving substitution of transition-metal centers and control of the flexible molecular architecture are likely to exist in other molecule-based multiferroics.},
doi = {10.1021/acs.inorgchem.8b01609},
url = {https://www.osti.gov/biblio/1467345}, journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 18,
volume = 57,
place = {United States},
year = {2018},
month = {8}
}

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