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Title: Pressure-induced magnetic crossover driven by hydrogen bonding in CuF2(H2O)2(3-chloropyridine)

Abstract

Here, hydrogen bonding plays a foundational role in the life, earth, and chemical sciences, with its richness and strength depending on the situation. In molecular materials, these interactions determine assembly mechanisms, control superconductivity, and even permit magnetic exchange. In spite of its long-standing importance, exquisite control of hydrogen bonding in molecule-based magnets has only been realized in limited form and remains as one of the major challenges. Here, we report the discovery that pressure can tune the dimensionality of hydrogen bonding networks in CuF2(H2O)2(3-chloropyridine) to induce magnetic switching. Specifically, we reveal how the development of exchange pathways under compression combined with an enhanced ab-plane hydrogen bonding network yields a three dimensional superexchange web between copper centers that triggers a reversible magnetic crossover. Similar pressure- and strain-driven crossover mechanisms involving coordinated motion of hydrogen bond networks may play out in other quantum magnets.

Authors:
 [1];  [2];  [1];  [3];  [4];  [5];  [6];  [4];  [7];  [1]
+ Show Author Affiliations
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. Univ. of Tennessee, Knoxville, TN (United States); Univ. of Florida, Gainesville, FL (United States)
  3. Carnegie Institution of Washington, Washington, D.C. (United States); Jilin Univ., Changchun (China)
  4. Virginia Commonwealth Univ., Richmond, VA (United States)
  5. Argonne National Lab. (ANL), Lemont, IL (United States); National Science Foundation, Arlington, VA (United States)
  6. Virginia Commonwealth Univ., Richmond, VA (United States); Center for Applied Physics and Technology of Peking Univ., Beijing (China)
  7. Carnegie Institution of Washington, Washington, D.C. (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1253598
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 4; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical physics; infrared spectroscopy; Raman spectroscopy

Citation Formats

O'Neal, Kenneth R., Brinzari, Tatiana V., Wright, Joshua B., Ma, Chunli, Giri, Santanab, Schlueter, John A., Wang, Qian, Jena, Puru, Liu, Zhenxian, and Musfeldt, Janice L. Pressure-induced magnetic crossover driven by hydrogen bonding in CuF2(H2O)2(3-chloropyridine). United States: N. p., 2014. Web. doi:10.1038/srep06054.
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O'Neal, Kenneth R., Brinzari, Tatiana V., Wright, Joshua B., Ma, Chunli, Giri, Santanab, Schlueter, John A., Wang, Qian, Jena, Puru, Liu, Zhenxian, & Musfeldt, Janice L. Pressure-induced magnetic crossover driven by hydrogen bonding in CuF2(H2O)2(3-chloropyridine). United States. https://doi.org/10.1038/srep06054
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O'Neal, Kenneth R., Brinzari, Tatiana V., Wright, Joshua B., Ma, Chunli, Giri, Santanab, Schlueter, John A., Wang, Qian, Jena, Puru, Liu, Zhenxian, and Musfeldt, Janice L. Wed . "Pressure-induced magnetic crossover driven by hydrogen bonding in CuF2(H2O)2(3-chloropyridine)". United States. https://doi.org/10.1038/srep06054. https://www.osti.gov/servlets/purl/1253598.
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@article{osti_1253598,
title = {Pressure-induced magnetic crossover driven by hydrogen bonding in CuF2(H2O)2(3-chloropyridine)},
author = {O'Neal, Kenneth R. and Brinzari, Tatiana V. and Wright, Joshua B. and Ma, Chunli and Giri, Santanab and Schlueter, John A. and Wang, Qian and Jena, Puru and Liu, Zhenxian and Musfeldt, Janice L.},
abstractNote = {Here, hydrogen bonding plays a foundational role in the life, earth, and chemical sciences, with its richness and strength depending on the situation. In molecular materials, these interactions determine assembly mechanisms, control superconductivity, and even permit magnetic exchange. In spite of its long-standing importance, exquisite control of hydrogen bonding in molecule-based magnets has only been realized in limited form and remains as one of the major challenges. Here, we report the discovery that pressure can tune the dimensionality of hydrogen bonding networks in CuF2(H2O)2(3-chloropyridine) to induce magnetic switching. Specifically, we reveal how the development of exchange pathways under compression combined with an enhanced ab-plane hydrogen bonding network yields a three dimensional superexchange web between copper centers that triggers a reversible magnetic crossover. Similar pressure- and strain-driven crossover mechanisms involving coordinated motion of hydrogen bond networks may play out in other quantum magnets.},
doi = {10.1038/srep06054},
journal = {Scientific Reports},
number = ,
volume = 4,
place = {United States},
year = {Wed Aug 13 00:00:00 EDT 2014},
month = {Wed Aug 13 00:00:00 EDT 2014}
}
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https://doi.org/10.1038/srep06054
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Works referenced in this record:

Complexity in Strongly Correlated Electronic Systems
journal, July 2005

Magnetoelectric phase diagrams of orthorhombic R MnO 3 ( R = Gd , Tb, and Dy)
journal, June 2005

Molecules to build solids: high TC molecule-based magnets by design and recent revival of cyano complexes chemistry
journal, September 1999

Magnetic field effects on the far-infrared absorption in Mn 12 -acetate
journal, May 2001

Preparation, crystal structure and magnetic properties of Ni2(dpa)2(pyz)(H2O)4
journal, May 2011

Magnetoelectric effects in an organometallic quantum magnet
journal, April 2011

Recent Developments in Low-Dimensional Copper(II) Molecular Magnets
journal, March 2013

  • Landee, Christopher P.; Turnbull, Mark M.
  • European Journal of Inorganic Chemistry, Vol. 2013, Issue 13
  • DOI: 10.1002/ejic.201300133

Thermal-, Pressure- and Light-Induced Spin-Crossover Behaviour in the Two-Dimensional Hofmann-Like Coordination Polymer [Fe(3-Clpy) 2 Pd(CN) 4 ]
journal, January 2013

  • Martínez, Víctor; Arcís Castillo, Zulema; Muñoz, M. Carmen
  • European Journal of Inorganic Chemistry, Vol. 2013, Issue 5-6
  • DOI: 10.1002/ejic.201201097

[Co(NCS)2(1,2-bis(2-pyridyl)ethylene)]n: A new 1D coordination polymer that shows a metamagnetic transition
journal, October 2013

Quantum Critical Transition Amplifies Magnetoelastic Coupling in Mn [ N ( CN ) 2 ] 2
journal, June 2013

Hydrogen Bonding and Multiphonon Structure in Copper Pyrazine Coordination Polymers
journal, October 2007

  • Brown, S.; Cao, J.; Musfeldt, J. L.
  • Inorganic Chemistry, Vol. 46, Issue 21
  • DOI: 10.1021/ic070122t

Pressure-Induced Sequential Orbital Reorientation in a Magnetic Framework Material
journal, September 2010

  • Halder, Gregory J.; Chapman, Karena W.; Schlueter, John A.
  • Angewandte Chemie International Edition, Vol. 50, Issue 2
  • DOI: 10.1002/anie.201003380

Pressure Effects on the Quasi-1-D Molecular Ferromagnet 2-(4,5,6,7-Tetrafluorobenzimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro- 1H -imidazole-3-oxide-1-oxyl
journal, October 2011

  • Seber, Gonca; Halder, Gregory J.; Schlueter, John A.
  • Crystal Growth & Design, Vol. 11, Issue 10
  • DOI: 10.1021/cg200802c

Pressure-Driven Orbital Reorientations and Coordination-Sphere Reconstructions in [CuF2(H2O)2(pyz)]
journal, May 2012

  • Prescimone, Alessandro; Morien, Chelsey; Allan, David
  • Angewandte Chemie International Edition, Vol. 51, Issue 30
  • DOI: 10.1002/anie.201202367

Importance of Halogen···Halogen Contacts for the Structural and Magnetic Properties of CuX 2 (pyrazine- N , N ′-dioxide)(H 2 O) 2 (X = Cl and Br)
journal, January 2012

  • Schlueter, John A.; Park, Hyunsoo; Halder, Gregory J.
  • Inorganic Chemistry, Vol. 51, Issue 4
  • DOI: 10.1021/ic201924q

Pressure-Induced Phase Transitions in Ammonium Squarate: A Supramolecular Structure Based on Hydrogen-Bonding and π-Stacking Interactions
journal, July 2011

  • Li, Shourui; Wang, Kai; Zhou, Mi
  • The Journal of Physical Chemistry B, Vol. 115, Issue 29
  • DOI: 10.1021/jp202975q

The magnetic exchange interaction via N–H⋯O-bonding in copper(II) complex with 1-phenyl-3-methyl-4-formylpyrazol-5-one 2-quinolylhydrazone
journal, August 2013

  • Levchenkov, Sergey I.; Shcherbakov, Igor N.; Popov, Leonid D.
  • Inorganica Chimica Acta, Vol. 405
  • DOI: 10.1016/j.ica.2013.05.032

High-Temperature and Pressure-Induced Ferroelectricity in Hydrogen-Bonded Supramolecular Crystals of Anilic Acids and 2,3-Di(2-pyridinyl)pyrazine
journal, March 2013

  • Horiuchi, Sachio; Kumai, Reiji; Tokura, Yoshinori
  • Journal of the American Chemical Society, Vol. 135, Issue 11
  • DOI: 10.1021/ja400318v

ESR of coupled spin-1/2 chains in copper pyrazine dinitrate: unveiling geometrical frustration
journal, December 2013

Review: A gentle introduction to magnetism: units, fields, theory, and experiment
journal, February 2014

Magnetic Interactions in Molecules and Highly Correlated Materials: Physical Content, Analytical Derivation, and Rigorous Extraction of Magnetic Hamiltonians
journal, September 2013

  • Malrieu, Jean Paul; Caballol, Rosa; Calzado, Carmen J.
  • Chemical Reviews, Vol. 114, Issue 1
  • DOI: 10.1021/cr300500z

Antiferromagnetic ordering through a hydrogen-bonded network in the molecular solid CuF 2 (H 2 O) 2 (3-chloropyridine)
journal, January 2013

  • Lapidus, Saul H.; Manson, Jamie L.; Park, Hyunsoo
  • Chem. Commun., Vol. 49, Issue 5
  • DOI: 10.1039/C2CC37444G

Magnetoelastic coupling in [Ru 2 (O 2 CMe) 4 ] 3 [Cr(CN) 6 ] molecule-based magnet
journal, December 2012

Magnetoelastic interactions in Raman spectra of Ho1−xNdxFe3(BO3)4 crystals
journal, November 2013

  • Krylov, Alexander S.; Sofronova, Svetlana N.; Gudim, Irina A.
  • Solid State Communications, Vol. 174
  • DOI: 10.1016/j.ssc.2013.09.011

An infrared and Raman spectroscopic study of gypsum at high pressures
journal, October 2001

  • Knittle, E.; Phillips, W.; Williams, Q.
  • Physics and Chemistry of Minerals, Vol. 28, Issue 9
  • DOI: 10.1007/s002690100187

Determination of molybdenum-oxygen bond distances and bond orders by Raman spectroscopy
journal, October 1990

  • Hardcastle, Franklin D.; Wachs, Israel E.
  • Journal of Raman Spectroscopy, Vol. 21, Issue 10
  • DOI: 10.1002/jrs.1250211009

Some Thoughts about Bond Energies, Bond Lengths, and Force Constants
journal, April 2000

  • Cremer, Dieter; Wu, Anan; Larsson, Andreas
  • Journal of Molecular Modeling, Vol. 6, Issue 4
  • DOI: 10.1007/PL00010739

Magnetoelastic phase transitions in the LuFe4Ge2 and YFe4Si2 compounds: A neutron diffraction study
journal, November 2012

  • Schobinger-Papamantellos, P.; Buschow, K. H. J.; Rodríguez-Carvajal, J.
  • Journal of Magnetism and Magnetic Materials, Vol. 324, Issue 22
  • DOI: 10.1016/j.jmmm.2012.05.058

Driving Magnetostructural Transitions in Layered Intermetallic Compounds
journal, May 2013

Switching of Molecular Spin States in Inorganic Complexes by Temperature, Pressure, Magnetic Field and Light: Towards Molecular Devices: Switching of Molecular Spin States in Inorganic Complexes
journal, November 2004

  • Bousseksou, Azzedine; Molnár, Gábor; Matouzenko, Galina
  • European Journal of Inorganic Chemistry, Vol. 2004, Issue 22
  • DOI: 10.1002/ejic.200400571

A Room-Temperature Molecular/Organic-Based Magnet
journal, June 1991

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
journal, June 1978

  • Mao, H. K.; Bell, P. M.; Shaner, J. W.
  • Journal of Applied Physics, Vol. 49, Issue 6
  • DOI: 10.1063/1.325277

High-power terahertz radiation from relativistic electrons
journal, November 2002

  • Carr, G. L.; Martin, Michael C.; McKinney, Wayne R.
  • Nature, Vol. 420, Issue 6912
  • DOI: 10.1038/nature01175

Pressure-Driven Orbital Reorientations and Coordination-Sphere Reconstructions in [CuF2(H2O)2(pyz)]
journal, May 2012

  • Prescimone, Alessandro; Morien, Chelsey; Allan, David
  • Angewandte Chemie, Vol. 124, Issue 30
  • DOI: 10.1002/ange.201202367

Pressure-Induced Sequential Orbital Reorientation in a Magnetic Framework Material
journal, September 2010

  • Halder, Gregory J.; Chapman, Karena W.; Schlueter, John A.
  • Angewandte Chemie, Vol. 123, Issue 2
  • DOI: 10.1002/ange.201003380

Recent Developments in Low-Dimensional Copper(II) Molecular Magnets
journal, April 2013

  • Landee, Christopher P.; Turnbull, Mark M.
  • European Journal of Inorganic Chemistry, Vol. 2013, Issue 13
  • DOI: 10.1002/ejic.201300268

Switching of Molecular Spin States in Inorganic Complexes by Temperature, Pressure, Magnetic Field and Light: Towards Molecular Devices
journal, February 2005

  • Bousseksou, Azzedine; Molnar, Gabor; Matouzenko, Galina
  • ChemInform, Vol. 36, Issue 6
  • DOI: 10.1002/chin.200506233

Magnetoelectric effects in an organo-metallic quantum magnet
text, January 2010

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    • Chemistry - A European Journal, Vol. 23, Issue 29
    • DOI: 10.1002/chem.201700591

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    journal, January 2016

    • Zhang, Weiquan; Wang, Dianpeng; Zhu, Lin
    • Dalton Transactions, Vol. 45, Issue 26
    • DOI: 10.1039/c6dt01363e

    Ternary and binary copper(II) complexes: synthesis, characterization, ROS-inductive, proteasome inhibitory, and anticancer properties
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    Epoxy Nanocomposites
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    • DOI: 10.7892/boris.97780
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