skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Magnetic ordering-induced multiferroic behavior in [CH 3NH 3][Co(HCOO) 3] metal-organic framework.

Abstract

Here, we present the first example of magnetic ordering-induced multiferroic behavior in a metal–organic framework magnet. This compound is [CH 3NH 3][Co(HCOO) 3] with a perovskite-like structure. The A-site [CH 3NH 3] + cation strongly distorts the framework, allowing anisotropic magnetic and electric behavior and coupling between them to occur. This material is a spin canted antiferromagnet below 15.9 K with a weak ferromagnetic component attributable to Dzyaloshinskii–Moriya (DM) interactions and experiences a discontinuous hysteretic magnetic-field-induced switching along [010] and a more continuous hysteresis along [101]. Coupling between the magnetic and electric order is resolved when the field is applied along this [101]: a spin rearrangement occurs at a critical magnetic field in the ac plane that induces a change in the electric polarization along [101] and [10-1]. The electric polarization exhibits an unusual memory effect, as it remembers the direction of the previous two magnetic-field pulses applied. The data are consistent with an inverse-DM mechanism for multiferroic behavior.

Authors:
 [1];  [2];  [1];  [3];  [1];  [1];  [1];  [2]
  1. Univ. of Coruna, Coruna (Spain)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Univ. of Santiago de Compostela, Santiago de Compostela (Spain)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1296677
Report Number(s):
LA-UR-15-28719
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 4; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; high magnetic field science

Citation Formats

Gomez-Aguirre, Lilian Claudia, Zapf, Vivien S., Pato-Doldan, Breogan, Mira, Jorge, Castro-Garcia, Socorro, Senaris-Rodriguez, Maria Antonia, Sanchez-Andujara, Manuel, and Singleton, John. Magnetic ordering-induced multiferroic behavior in [CH3NH3][Co(HCOO)3] metal-organic framework.. United States: N. p., 2015. Web. doi:10.1021/jacs.5b11688.
Gomez-Aguirre, Lilian Claudia, Zapf, Vivien S., Pato-Doldan, Breogan, Mira, Jorge, Castro-Garcia, Socorro, Senaris-Rodriguez, Maria Antonia, Sanchez-Andujara, Manuel, & Singleton, John. Magnetic ordering-induced multiferroic behavior in [CH3NH3][Co(HCOO)3] metal-organic framework.. United States. doi:10.1021/jacs.5b11688.
Gomez-Aguirre, Lilian Claudia, Zapf, Vivien S., Pato-Doldan, Breogan, Mira, Jorge, Castro-Garcia, Socorro, Senaris-Rodriguez, Maria Antonia, Sanchez-Andujara, Manuel, and Singleton, John. Wed . "Magnetic ordering-induced multiferroic behavior in [CH3NH3][Co(HCOO)3] metal-organic framework.". United States. doi:10.1021/jacs.5b11688. https://www.osti.gov/servlets/purl/1296677.
@article{osti_1296677,
title = {Magnetic ordering-induced multiferroic behavior in [CH3NH3][Co(HCOO)3] metal-organic framework.},
author = {Gomez-Aguirre, Lilian Claudia and Zapf, Vivien S. and Pato-Doldan, Breogan and Mira, Jorge and Castro-Garcia, Socorro and Senaris-Rodriguez, Maria Antonia and Sanchez-Andujara, Manuel and Singleton, John},
abstractNote = {Here, we present the first example of magnetic ordering-induced multiferroic behavior in a metal–organic framework magnet. This compound is [CH3NH3][Co(HCOO)3] with a perovskite-like structure. The A-site [CH3NH3]+ cation strongly distorts the framework, allowing anisotropic magnetic and electric behavior and coupling between them to occur. This material is a spin canted antiferromagnet below 15.9 K with a weak ferromagnetic component attributable to Dzyaloshinskii–Moriya (DM) interactions and experiences a discontinuous hysteretic magnetic-field-induced switching along [010] and a more continuous hysteresis along [101]. Coupling between the magnetic and electric order is resolved when the field is applied along this [101]: a spin rearrangement occurs at a critical magnetic field in the ac plane that induces a change in the electric polarization along [101] and [10-1]. The electric polarization exhibits an unusual memory effect, as it remembers the direction of the previous two magnetic-field pulses applied. The data are consistent with an inverse-DM mechanism for multiferroic behavior.},
doi = {10.1021/jacs.5b11688},
journal = {Journal of the American Chemical Society},
number = 4,
volume = 138,
place = {United States},
year = {2015},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 53 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Giant Room-Temperature Magnetodielectric Response in a MOF at 0.1 Tesla
journal, October 2017


Coupling of Magnetic and Elastic Domains in the Organic-Inorganic Layered Perovskite-Like (C 6 H 5 C 2 H 4 NH 3 ) 2 Fe II Cl 4 Crystal
journal, July 2017

  • Nakayama, Yuki; Nishihara, Sadafumi; Inoue, Katsuya
  • Angewandte Chemie International Edition, Vol. 56, Issue 32
  • DOI: 10.1002/anie.201703898

Coexistence of Three Ferroic Orders in the Multiferroic Compound [(CH 3 ) 4 N][Mn(N 3 ) 3 ] with Perovskite-Like Structure
journal, April 2016

  • Gómez-Aguirre, L. Claudia; Pato-Doldán, Breogán; Stroppa, Alessandro
  • Chemistry - A European Journal, Vol. 22, Issue 23
  • DOI: 10.1002/chem.201503445

A Variety of Phase-Transition Behaviors in a Niccolite Series of [NH 3 (CH 2 ) 4 NH 3 ][M(HCOO) 3 ] 2
journal, March 2016

  • Shang, Ran; Chen, Sa; Hu, Ke-Li
  • Chemistry - A European Journal, Vol. 22, Issue 18
  • DOI: 10.1002/chem.201600689

A Series of Bimetallic Ammonium AlNa Formates
journal, June 2017


Microscopic Insights on the Multiferroic Perovskite-Like [CH 3 NH 3 ][Co(COOH) 3 ] Compound
journal, October 2017

  • Mazzuca, Lidia; Cañadillas-Delgado, Laura; Fabelo, Oscar
  • Chemistry - A European Journal, Vol. 24, Issue 2
  • DOI: 10.1002/chem.201703140

3D Organic–Inorganic Perovskite Ferroelastic Materials with Two Ferroelastic Phases: [Et 3 P(CH 2 ) 2 F][Mn(dca) 3 ] and [Et 3 P(CH 2 ) 2 Cl][Mn(dca) 3 ]
journal, April 2019

  • Zhao, Meng‐Meng; Zhou, Lin; Shi, Ping‐Ping
  • Chemistry – A European Journal, Vol. 25, Issue 25
  • DOI: 10.1002/chem.201900771

Formation of the layered conductive magnet CrCl2(pyrazine)2 through redox-active coordination chemistry
journal, September 2018

  • Pedersen, Kasper S.; Perlepe, Panagiota; Aubrey, Michael L.
  • Nature Chemistry, Vol. 10, Issue 10
  • DOI: 10.1038/s41557-018-0107-7

Three coordination frameworks with copper formate based low dimensional motifs: synthesis, structure and magnetic properties
journal, January 2017

  • Bovill, Sally M.; Dixey, Richard J. C.; Saines, Paul J.
  • CrystEngComm, Vol. 19, Issue 13
  • DOI: 10.1039/c6ce01601d

Structural distortions in the high-pressure polar phases of ammonium metal formates
journal, January 2016

  • Collings, Ines E.; Bykov, Maxim; Bykova, Elena
  • CrystEngComm, Vol. 18, Issue 46
  • DOI: 10.1039/c6ce01891b

Effect of solvent, temperature and pressure on the stability of chiral and perovskite metal formate frameworks of [NH 2 NH 3 ][M(HCOO) 3 ] (M = Mn, Fe, Zn)
journal, January 2016

  • Mączka, Mirosław; Pasińska, Katarzyna; Ptak, Maciej
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 46
  • DOI: 10.1039/c6cp06648h

Multiple phase and dielectric transitions on a novel multi-sensitive [TPrA][M(dca) 3 ] (M: Fe 2+ , Co 2+ and Ni 2+ ) hybrid inorganic–organic perovskite family
journal, January 2016

  • Bermúdez-García, J. M.; Sánchez-Andújar, M.; Yáñez-Vilar, S.
  • Journal of Materials Chemistry C, Vol. 4, Issue 22
  • DOI: 10.1039/c6tc00723f

Importing spontaneous polarization into a Heisenberg ferromagnet for a potential single-phase multiferroic
journal, January 2016

  • Huang, Bo; Wang, Bao-Ying; Du, Zi-Yi
  • Journal of Materials Chemistry C, Vol. 4, Issue 37
  • DOI: 10.1039/c6tc02715f

Magnetic transitions and isotropic versus anisotropic magnetic behaviour of [CH 3 NH 3 ][M(HCOO) 3 ] M = Mn 2+ , Co 2+ , Ni 2+ , Cu 2+ metal–organic perovskites
journal, January 2016

  • Pato-Doldán, B.; Gómez-Aguirre, L. C.; Hansen, A. P.
  • Journal of Materials Chemistry C, Vol. 4, Issue 47
  • DOI: 10.1039/c6tc03992h

Zn( ii )-based metal–organic framework: an exceptionally thermally stable, guest-free low dielectric material
journal, January 2017

  • Mendiratta, Shruti; Usman, Muhammad; Chang, Chun-Chi
  • Journal of Materials Chemistry C, Vol. 5, Issue 6
  • DOI: 10.1039/c6tc05314a

Synthesis and temperature-dependent studies of a perovskite-like manganese formate framework templated with protonated acetamidine
journal, January 2017

  • Mączka, Mirosław; Janczak, Jan; Trzebiatowska, Monika
  • Dalton Transactions, Vol. 46, Issue 26
  • DOI: 10.1039/c7dt01251a

Thermal conductivity of a perovskite-type metal–organic framework crystal
journal, January 2017

  • Gunatilleke, Wilarachchige D. C. B.; Wei, Kaya; Niu, Zheng
  • Dalton Transactions, Vol. 46, Issue 39
  • DOI: 10.1039/c7dt02927f

Magnetodielectric coupling in a non-perovskite metal–organic framework
journal, January 2017

  • Basu, Tathamay; Jesche, Anton; Bredenkötter, Björn
  • Mater. Horiz., Vol. 4, Issue 6
  • DOI: 10.1039/c7mh00716g

Study of the relationship between magnetic field and dielectric properties in two ferromagnetic complexes
journal, January 2017


Giant barocaloric tunability in [(CH 3 CH 2 CH 2 ) 4 N]Cd[N(CN) 2 ] 3 hybrid perovskite
journal, January 2018

  • Bermúdez-García, Juan Manuel; Yáñez-Vilar, Susana; García-Fernández, Alberto
  • Journal of Materials Chemistry C, Vol. 6, Issue 37
  • DOI: 10.1039/c7tc03136j

Disorder–order transitions in the perovskite metal–organic frameworks [(CH 3 ) 2 NH 2 ][M(HCOO) 3 ] at high pressure
journal, January 2018

  • Collings, Ines E.; Bykov, Maxim; Bykova, Elena
  • CrystEngComm, Vol. 20, Issue 25
  • DOI: 10.1039/c8ce00617b

Magnetic layered perovskites of [CH 3 C(NH 2 ) 2 ] 2 [M(HCOO) 4 ] (M = Co 2+ and Ni 2+ ): synthesis, structures and properties
journal, January 2018

  • Liu, Shu; Wang, Bing-Wu; Wang, Zhe-Ming
  • Dalton Transactions, Vol. 47, Issue 34
  • DOI: 10.1039/c8dt01729h

Two-dimensional magnetic materials of cobalt( ii ) triangular lattices constructed by a mixed benzimidazole–dicarboxylate strategy
journal, January 2019

  • Kong, Jiao-Jiao; Jiang, Yu-Xuan; Zhang, Jia-Chen
  • CrystEngComm, Vol. 21, Issue 15
  • DOI: 10.1039/c9ce00129h

Raman and single-crystal X-ray diffraction evidence of pressure-induced phase transitions in a perovskite-like framework of [(C 3 H 7 ) 4 N] [Mn(N(CN) 2 ) 3 ]
journal, January 2019

  • Mączka, Mirosław; Collings, Ines E.; Leite, Fabio Furtado
  • Dalton Transactions, Vol. 48, Issue 25
  • DOI: 10.1039/c9dt01648a

Electric and magnetic transitions with 90° turning of polarizations in a layered perovskite of [NH 4 Cl] 2 [Ni(HCOO) 2 (NH 3 ) 2 ]
journal, November 2018

  • Chen, Sa; Shang, Ran; Wang, Bing-Wu
  • APL Materials, Vol. 6, Issue 11
  • DOI: 10.1063/1.5040688

Incommensurate structures of the [CH 3 NH 3 ][Co(COOH) 3 ] compound
journal, January 2019