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Title: Magnetic transitions and isotropic versus anisotropic magnetic behaviour of [CH3NH3][M(HCOO)3] M = Mn2+, Co2+, Ni2+, Cu2+ metal–organic perovskites

Abstract

We show unconventional magnetic features of the [CH3NH3][M(HCOO)3] perovskite-like family such as the isotropic/anisotropic response unmasked by high magnetic fields.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3];  [1];  [1];  [1];  [2];  [2]
  1. Univ. of A Coruna, A Coruna (Spain)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Univ. of Santiago de Compostela (Spain)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1417166
Report Number(s):
LA-UR-17-28056
Journal ID: ISSN 2050-7526; JMCCCX; TRN: US1800997
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry C
Additional Journal Information:
Journal Volume: 4; Journal Issue: 47; Journal ID: ISSN 2050-7526
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; High Magnetic Field Science

Citation Formats

Pato-Doldan, Breogan, Gomez-Aguirre, L. C., Hansen, A. P., Mira, J., Castro-Garcia, S., Sanchez-Andujar, M., Senaris-Rodriguez, M. A., Zapf, V. S., and Singleton, J. Magnetic transitions and isotropic versus anisotropic magnetic behaviour of [CH3NH3][M(HCOO)3] M = Mn2+, Co2+, Ni2+, Cu2+ metal–organic perovskites. United States: N. p., 2016. Web. doi:10.1039/C6TC03992H.
Pato-Doldan, Breogan, Gomez-Aguirre, L. C., Hansen, A. P., Mira, J., Castro-Garcia, S., Sanchez-Andujar, M., Senaris-Rodriguez, M. A., Zapf, V. S., & Singleton, J. Magnetic transitions and isotropic versus anisotropic magnetic behaviour of [CH3NH3][M(HCOO)3] M = Mn2+, Co2+, Ni2+, Cu2+ metal–organic perovskites. United States. doi:10.1039/C6TC03992H.
Pato-Doldan, Breogan, Gomez-Aguirre, L. C., Hansen, A. P., Mira, J., Castro-Garcia, S., Sanchez-Andujar, M., Senaris-Rodriguez, M. A., Zapf, V. S., and Singleton, J. Mon . "Magnetic transitions and isotropic versus anisotropic magnetic behaviour of [CH3NH3][M(HCOO)3] M = Mn2+, Co2+, Ni2+, Cu2+ metal–organic perovskites". United States. doi:10.1039/C6TC03992H. https://www.osti.gov/servlets/purl/1417166.
@article{osti_1417166,
title = {Magnetic transitions and isotropic versus anisotropic magnetic behaviour of [CH3NH3][M(HCOO)3] M = Mn2+, Co2+, Ni2+, Cu2+ metal–organic perovskites},
author = {Pato-Doldan, Breogan and Gomez-Aguirre, L. C. and Hansen, A. P. and Mira, J. and Castro-Garcia, S. and Sanchez-Andujar, M. and Senaris-Rodriguez, M. A. and Zapf, V. S. and Singleton, J.},
abstractNote = {We show unconventional magnetic features of the [CH3NH3][M(HCOO)3] perovskite-like family such as the isotropic/anisotropic response unmasked by high magnetic fields.},
doi = {10.1039/C6TC03992H},
journal = {Journal of Materials Chemistry C},
number = 47,
volume = 4,
place = {United States},
year = {2016},
month = {10}
}

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Cited by: 5 works
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Works referenced in this record:

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Anionic NaCl-type frameworks of [Mn II (HCOO) 3 ], templated by alkylammonium, exhibit weak ferromagnetism
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Ferroelasticity in a metal–organic framework perovskite; towards a new class of multiferroics
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Compositional dependence of anomalous thermal expansion in perovskite-like ABX 3 formates
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Diamagnetic Corrections and Pascal's Constants
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Polarized Neutron Diffraction to Probe Local Magnetic Anisotropy of a Low-Spin Fe(III) Complex
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A Multiferroic Perdeutero Metal-Organic Framework
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Magnetic Ordering-Induced Multiferroic Behavior in [CH 3 NH 3 ][Co(HCOO) 3 ] Metal–Organic Framework
journal, January 2016

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  • Journal of the American Chemical Society, Vol. 138, Issue 4
  • DOI: 10.1021/jacs.5b11688

Magnetic Structure and Exchange Interactions in Quasi-One-Dimensional MnCl 2 (urea) 2
journal, December 2015


Solid-state principles applied to organic–inorganic perovskites: new tricks for an old dog
journal, January 2014

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  • Chem. Sci., Vol. 5, Issue 12
  • DOI: 10.1039/C4SC02211D

There's Room in the Middle
journal, October 2007


Order−Disorder Antiferroelectric Phase Transition in a Hybrid Inorganic−Organic Framework with the Perovskite Architecture
journal, August 2008

  • Jain, Prashant; Dalal, Naresh S.; Toby, Brian H.
  • Journal of the American Chemical Society, Vol. 130, Issue 32
  • DOI: 10.1021/ja801952e

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

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Magnetoelectric coupling in the paramagnetic state of a metal-organic framework
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Cross coupling between electric and magnetic orders in a multiferroic metal-organic framework
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Multiferroic Materials: The Attractive Approach of Metal-Organic Frameworks (MOFs)
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Vibrational properties and DFT calculations of the perovskite metal formate framework of [(CH3)2NH2][Ni(HCOO3)] system
journal, July 2014

  • Mączka, M.; Zierkiewicz, W.; Michalska, D.
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 128
  • DOI: 10.1016/j.saa.2014.03.006

An extended Tolerance Factor approach for organic–inorganic perovskites
journal, January 2015

  • Kieslich, Gregor; Sun, Shijing; Cheetham, Anthony K.
  • Chemical Science, Vol. 6, Issue 6
  • DOI: 10.1039/C5SC00961H

Phase Transitions, Prominent Dielectric Anomalies, and Negative Thermal Expansion in Three High Thermally Stable Ammonium Magnesium-Formate Frameworks
journal, December 2013

  • Shang, Ran; Xu, Guan-Cheng; Wang, Zhe-Ming
  • Chemistry - A European Journal, Vol. 20, Issue 4
  • DOI: 10.1002/chem.201303425

Near room temperature dielectric transition in the perovskite formate framework [(CH3)2NH2][Mg(HCOO)3]
journal, January 2012

  • Pato-Doldán, B.; Sánchez-Andújar, M.; Gómez-Aguirre, L. C.
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 24
  • DOI: 10.1039/c2cp40564d

Elastic relaxation behavior, magnetoelastic coupling, and order-disorder processes in multiferroic metal-organic frameworks
journal, December 2012


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
  • DOI: 10.1002/anie.201101405

Ab-initio structure determination of LiSbWO6 by X-ray powder diffraction
journal, March 1988


Hybrid Improper Ferroelectricity in a Multiferroic and Magnetoelectric Metal-Organic Framework
journal, February 2013


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
  • DOI: 10.1021/ja904156s

Mechanism of the order-disorder phase transition, and glassy behavior in the metal-organic framework [(CH3)2NH2]Zn(HCOO)3
journal, April 2011

  • Besara, T.; Jain, P.; Dalal, N. S.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 17
  • DOI: 10.1073/pnas.1102079108

Metal–organic frameworks: a new class of porous materials
journal, August 2004


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
  • DOI: 10.1021/ic0498081

Irreversible transformation of chiral to achiral polymorph of K[Co(HCOO)3]: synthesis, structures, and magnetic properties
journal, January 2011

  • Duan, Zhiming; Wang, Zheming; Gao, Song
  • Dalton Transactions, Vol. 40, Issue 17
  • DOI: 10.1039/c0dt01701a

Dynamics of Coupled Quantum Spin Chains
journal, September 1996


Magnetic behavior of the metal organic framework [(CH 3 ) 2 NH 2 ]Co(HCOO) 3
journal, January 2015

  • Vinod, K.; Deepak, C. S.; Sharma, Shilpam
  • RSC Advances, Vol. 5, Issue 47
  • DOI: 10.1039/C5RA01417D

Probing ferroic transitions in a multiferroic framework family: a neutron diffraction study of the ammonium transition metal formates
journal, January 2015

  • Lawler, James M. M.; Manuel, Pascal; Thompson, Amber L.
  • Dalton Transactions, Vol. 44, Issue 25
  • DOI: 10.1039/C5DT00733J

Metal-Organic Perovskites: Synthesis, Structures, and Magnetic Properties of [C(NH 2 ) 3 ][M II (HCOO) 3 ] (M=Mn, Fe, Co, Ni, Cu, and Zn; C(NH 2 ) 3 = Guanidinium)
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  • DOI: 10.1002/chem.200901605

Separation of energy scales in the kagome antiferromagnet TmAgGe: A magnetic-field-orientation study up to 55 T
journal, March 2007


The crystal structure of dimethylammonium copper(II) formate, NH2(CH2)2[Cu(OOCH)3]
journal, September 1973

  • Sletten, E.; Jensen, L. H.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 29, Issue 9
  • DOI: 10.1107/S0567740873005480

A Multiferroic Perdeutero Metal-Organic Framework
journal, October 2011


Polarized Neutron Diffraction to Probe Local Magnetic Anisotropy of a Low-Spin Fe(III) Complex
journal, February 2016

  • Ridier, Karl; Mondal, Abhishake; Boilleau, Corentin
  • Angewandte Chemie, Vol. 128, Issue 12
  • DOI: 10.1002/ange.201511354

    Works referencing / citing this record:

    Hybrid Improper Ferroelectricity in a Multiferroic and Magnetoelectric Metal-Organic Framework
    journal, February 2013


    Multiferroic Materials: The Attractive Approach of Metal-Organic Frameworks (MOFs)
    journal, February 2010

    • Rogez, Guillaume; Viart, Nathalie; Drillon, Marc
    • Angewandte Chemie International Edition, Vol. 49, Issue 11
    • DOI: 10.1002/anie.200906660

    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
    • DOI: 10.1002/anie.201101405

    A Multiferroic Perdeutero Metal-Organic Framework
    journal, October 2011

    • Fu, Da-Wei; Zhang, Wen; Cai, Hong-Ling
    • Angewandte Chemie International Edition, Vol. 50, Issue 50
    • DOI: 10.1002/anie.201103265

    Polarized Neutron Diffraction to Probe Local Magnetic Anisotropy of a Low-Spin Fe(III) Complex
    journal, February 2016

    • Ridier, Karl; Mondal, Abhishake; Boilleau, Corentin
    • Angewandte Chemie International Edition, Vol. 55, Issue 12
    • DOI: 10.1002/anie.201511354

    Metal-Organic Perovskites: Synthesis, Structures, and Magnetic Properties of [C(NH 2 ) 3 ][M II (HCOO) 3 ] (M=Mn, Fe, Co, Ni, Cu, and Zn; C(NH 2 ) 3 = Guanidinium)
    journal, November 2009

    • Hu, Ke-Li; Kurmoo, Mohamedally; Wang, Zheming
    • Chemistry - A European Journal, Vol. 15, Issue 44
    • DOI: 10.1002/chem.200901605

    Phase Transitions, Prominent Dielectric Anomalies, and Negative Thermal Expansion in Three High Thermally Stable Ammonium Magnesium-Formate Frameworks
    journal, December 2013

    • Shang, Ran; Xu, Guan-Cheng; Wang, Zhe-Ming
    • Chemistry - A European Journal, Vol. 20, Issue 4
    • DOI: 10.1002/chem.201303425

    The quadratic-layer antiferromagnet
    journal, January 1970


    Ab-initio structure determination of LiSbWO6 by X-ray powder diffraction
    journal, March 1988


    Ferroelasticity in a metal–organic framework perovskite; towards a new class of multiferroics
    journal, August 2013


    Magnetic properties of six-coordinated high-spin cobalt(II) complexes: Theoretical background and its application
    journal, September 2008


    Ferroelectric metal organic framework (MOF)
    journal, December 2010


    Metal–organic frameworks: a new class of porous materials
    journal, August 2004


    Vibrational properties and DFT calculations of the perovskite metal formate framework of [(CH3)2NH2][Ni(HCOO3)] system
    journal, July 2014

    • Mączka, M.; Zierkiewicz, W.; Michalska, D.
    • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 128
    • DOI: 10.1016/j.saa.2014.03.006

    Magnetic Structure and Exchange Interactions in Quasi-One-Dimensional MnCl 2 (urea) 2
    journal, December 2015


    Diamagnetic Corrections and Pascal's Constants
    journal, April 2008

    • Bain, Gordon A.; Berry, John F.
    • Journal of Chemical Education, Vol. 85, Issue 4
    • DOI: 10.1021/ed085p532

    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
    • DOI: 10.1021/ic0498081

    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
    • DOI: 10.1021/ic901872g

    Order−Disorder Antiferroelectric Phase Transition in a Hybrid Inorganic−Organic Framework with the Perovskite Architecture
    journal, August 2008

    • Jain, Prashant; Dalal, Naresh S.; Toby, Brian H.
    • Journal of the American Chemical Society, Vol. 130, Issue 32
    • DOI: 10.1021/ja801952e

    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
    • DOI: 10.1021/ja904156s

    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
    • DOI: 10.1021/jacs.5b11688

    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
    • DOI: 10.1038/srep02024

    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
    • DOI: 10.1038/srep06062

    Anionic NaCl-type frameworks of [Mn II (HCOO) 3 ], templated by alkylammonium, exhibit weak ferromagnetism
    journal, January 2004

    • Wang, Zheming; Zhang, Bin; Otsuka, Takeo
    • Dalton Trans., Issue 15
    • DOI: 10.1039/b404466e

    Irreversible transformation of chiral to achiral polymorph of K[Co(HCOO)3]: synthesis, structures, and magnetic properties
    journal, January 2011

    • Duan, Zhiming; Wang, Zheming; Gao, Song
    • Dalton Transactions, Vol. 40, Issue 17
    • DOI: 10.1039/c0dt01701a

    Near room temperature dielectric transition in the perovskite formate framework [(CH3)2NH2][Mg(HCOO)3]
    journal, January 2012

    • Pato-Doldán, B.; Sánchez-Andújar, M.; Gómez-Aguirre, L. C.
    • Physical Chemistry Chemical Physics, Vol. 14, Issue 24
    • DOI: 10.1039/c2cp40564d

    Solid-state principles applied to organic–inorganic perovskites: new tricks for an old dog
    journal, January 2014

    • Kieslich, Gregor; Sun, Shijing; Cheetham, Anthony K.
    • Chem. Sci., Vol. 5, Issue 12
    • DOI: 10.1039/c4sc02211d

    Probing ferroic transitions in a multiferroic framework family: a neutron diffraction study of the ammonium transition metal formates
    journal, January 2015

    • Lawler, James M. M.; Manuel, Pascal; Thompson, Amber L.
    • Dalton Transactions, Vol. 44, Issue 25
    • DOI: 10.1039/c5dt00733j

    Compositional dependence of anomalous thermal expansion in perovskite-like ABX 3 formates
    journal, January 2016

    • Collings, Ines E.; Hill, Joshua A.; Cairns, Andrew B.
    • Dalton Transactions, Vol. 45, Issue 10
    • DOI: 10.1039/c5dt03263f

    Magnetic behavior of the metal organic framework [(CH 3 ) 2 NH 2 ]Co(HCOO) 3
    journal, January 2015

    • Vinod, K.; Deepak, C. S.; Sharma, Shilpam
    • RSC Advances, Vol. 5, Issue 47
    • DOI: 10.1039/c5ra01417d

    An extended Tolerance Factor approach for organic–inorganic perovskites
    journal, January 2015

    • Kieslich, Gregor; Sun, Shijing; Cheetham, Anthony K.
    • Chemical Science, Vol. 6, Issue 6
    • DOI: 10.1039/c5sc00961h

    Mechanism of the order-disorder phase transition, and glassy behavior in the metal-organic framework [(CH3)2NH2]Zn(HCOO)3
    journal, April 2011

    • Besara, T.; Jain, P.; Dalal, N. S.
    • Proceedings of the National Academy of Sciences, Vol. 108, Issue 17
    • DOI: 10.1073/pnas.1102079108

    Linear Magnetic Chains with Anisotropic Coupling
    journal, August 1964


    Separation of energy scales in the kagome antiferromagnet TmAgGe: A magnetic-field-orientation study up to 55 T
    journal, March 2007


    Elastic relaxation behavior, magnetoelastic coupling, and order-disorder processes in multiferroic metal-organic frameworks
    journal, December 2012


    Electron-Phonon and Magnetoelastic Interactions in Ferromagnetic Co [ N ( CN ) 2 ] 2
    journal, July 2013


    Dynamics of Coupled Quantum Spin Chains
    journal, September 1996


    Poly[methylammonium tris(μ 2 -formato-κ 2 O : O ′)cobalt(II)]
    journal, November 2004

    • Boča, Miroslav; Svoboda, Ingrid; Renz, Franz
    • Acta Crystallographica Section C Crystal Structure Communications, Vol. 60, Issue 12
    • DOI: 10.1107/s0108270104025776

    The crystal structure of dimethylammonium copper(II) formate, NH2(CH2)2[Cu(OOCH)3]
    journal, September 1973

    • Sletten, E.; Jensen, L. H.
    • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 29, Issue 9
    • DOI: 10.1107/s0567740873005480

    There's Room in the Middle
    journal, October 2007