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

Journal Article · · Inorganic Chemistry
 [1];  [1];  [1];  [2];  [3];  [4];  [3];  [2];  [5];  [4];  [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
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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.
Research Organization:
Los Alamos National Laboratory (LANL)
Sponsoring Organization:
Fok Ying Tung Education Foundation (China); LANL Laboratory Directed Research and Development (LDRD) Program; National Natural Science Foundation of China (NSFC); National Science Foundation (NSF) (United States); Qing Nian Ba Jian Program (China); Special Funds for Major State Basic Research (China); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC52-06NA25396
OSTI ID:
1467345
Report Number(s):
LA-UR-18-25204
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 18 Vol. 57; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Magnetic field-temperature phase diagram of multiferroic (NH4)2FeCl5·H2O journal August 2019
Elucidation of dipolar dynamics and the nature of structural phases in the [(CH 3 ) 2 NH 2 ][Zn(HCOO) 3 ] hybrid perovskite framework journal January 2019
First-principles study of the structural, electronic, magnetic, and ferroelectric properties of a charge-ordered iron( ii )-iron( iii ) formate framework journal September 2019
First-principles study of the structural, electronic, magnetic and ferroelectric properties of a charge ordered Iron(II)- Iron(III) formate framework text January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
High Magnetic Field Science