Enhancing easy-plane anisotropy in bespoke Ni(II) quantum magnets

Manson, Jamie L.; Manson, Zachary E.; Sargent, Ashley; Villa, Danielle Y.; Etten, Nicole L.; Blackmore, William J. A.; Curley, Samuel P. M.; Williams, Robert C.; Brambleby, Jamie; Goddard, Paul A.; Ozarowski, Andrew; Wilson, Murray N.; Huddart, Benjamin M.; Lancaster, Tom; Johnson, Roger D.; Blundell, Stephen J.; Bendix, Jesper; Wheeler, Kraig A.; Lapidus, Saul H.; Xiao, Fan; Birnbaum, Serena; Singleton, John

doi:10.1016/j.poly.2020.114379

Title: Enhancing easy-plane anisotropy in bespoke Ni(II) quantum magnets

Abstract

We examine the crystal structures and magnetic properties of several S = 1 Ni(II) coordination compounds, molecules and polymers, that include the bridging ligands HF₂^-, AF₆^2- (A = Ti, Zr) and pyrazine or non-bridging ligands F^-, SiF₆^2-, glycine, H₂O, 1-vinylimidazole, 4-methylpyrazole and 3-hydroxypyridine. Pseudo-octahedral NiN₄F₂, NiN₄O₂ or NiN₄OF cores consist of equatorial Ni-N bonds that are equal to or slightly longer than the axial Ni-L_ax bonds. By design, the zero-field splitting (D) is large in these systems and, in the presence of substantial exchange interactions (J), can be difficult to discriminate from magnetometry measurements on powder samples. Thus, we relied on pulsed-field magnetization in those cases and employed electron-spin resonance (ESR) to confirm D when J ← D. The anisotropy of each compound was found to be easy-plane (D > 0) and range from ≈ 8–25 K. This work reveals a linear correlation between the ratio d(Ni-L_ax)/d(Ni-N_eq) and D although the ligand spectrochemical properties may play an important role. We assert that this relationship allows us to predict the type of magnetocrystalline anisotropy in tailored Ni(II) quantum magnets.

Authors:

^[1]; Manson, Zachary E. ^[1]; Sargent, Ashley ^[1];

^[1];

^[2]; Curley, Samuel P. M. ^[2]; Williams, Robert C. ^[2]; Brambleby, Jamie ^[2];

^[2]; Ozarowski, Andrew ^[3]; Wilson, Murray N. ^[4];

^[4];

^[5];

^[5]; Bendix, Jesper ^[6]; Wheeler, Kraig A. ^[7]; Lapidus, Saul H. ^[8]; Xiao, Fan ^[9] more »

Eastern Washington Univ., Cheney, WA (United States)
Univ. of Warwick, Coventry (United Kingdom)
Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
Durham Univ. (United Kingdom). Center for Materials Physics
Univ. of Oxford (United Kingdom). Clarendon Lab.
Univ. of Copenhagen (Denmark)
Whitworth Univ., Spokane, WA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Paul Scherrer Inst., Villigen (Switzerland). Lab. for Neutron Scattering and Imaging; Univ. of Bern (Switzerland)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States). National High Magnetic Field Lab. (MagLab)

Publication Date:: Wed Jan 22 00:00:00 EST 2020

Research Org.:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Org.:: USDOE Office of Science (SC); National Science Foundation (NSF); Engineering and Physical Sciences Research Council (EPSRC)

OSTI Identifier:: 1645091

Report Number(s):: LA-UR-20-22868
Journal ID: ISSN 0277-5387; TRN: US2202962

Grant/Contract Number:: 89233218CNA000001; DMR-1703003; CHE-1827313; AC02-06CH1137; 681260; DMR-164477; EP/N023803/1; EP/N024028/1; EP/N032128/1

Resource Type:: Accepted Manuscript

Journal Name:: Polyhedron

Additional Journal Information:: Journal Volume: 180; Journal ID: ISSN 0277-5387

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Quantum magnetism; anisotropy; low-dimensional; high magnetic fields; nickel

Citation Formats


                    Manson, Jamie L., Manson, Zachary E., Sargent, Ashley, Villa, Danielle Y., Etten, Nicole L., Blackmore, William J. A., Curley, Samuel P. M., Williams, Robert C., Brambleby, Jamie, Goddard, Paul A., Ozarowski, Andrew, Wilson, Murray N., Huddart, Benjamin M., Lancaster, Tom, Johnson, Roger D., Blundell, Stephen J., Bendix, Jesper, Wheeler, Kraig A., Lapidus, Saul H., Xiao, Fan, Birnbaum, Serena, and Singleton, John. Enhancing easy-plane anisotropy in bespoke Ni(II) quantum magnets.  United States: N. p., 2020. 
Web.  doi:10.1016/j.poly.2020.114379.

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                    Manson, Jamie L., Manson, Zachary E., Sargent, Ashley, Villa, Danielle Y., Etten, Nicole L., Blackmore, William J. A., Curley, Samuel P. M., Williams, Robert C., Brambleby, Jamie, Goddard, Paul A., Ozarowski, Andrew, Wilson, Murray N., Huddart, Benjamin M., Lancaster, Tom, Johnson, Roger D., Blundell, Stephen J., Bendix, Jesper, Wheeler, Kraig A., Lapidus, Saul H., Xiao, Fan, Birnbaum, Serena, & Singleton, John. Enhancing easy-plane anisotropy in bespoke Ni(II) quantum magnets.  United States.  https://doi.org/10.1016/j.poly.2020.114379

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                    Manson, Jamie L., Manson, Zachary E., Sargent, Ashley, Villa, Danielle Y., Etten, Nicole L., Blackmore, William J. A., Curley, Samuel P. M., Williams, Robert C., Brambleby, Jamie, Goddard, Paul A., Ozarowski, Andrew, Wilson, Murray N., Huddart, Benjamin M., Lancaster, Tom, Johnson, Roger D., Blundell, Stephen J., Bendix, Jesper, Wheeler, Kraig A., Lapidus, Saul H., Xiao, Fan, Birnbaum, Serena, and Singleton, John. Wed .  
"Enhancing easy-plane anisotropy in bespoke Ni(II) quantum magnets".  United States.  https://doi.org/10.1016/j.poly.2020.114379.  https://www.osti.gov/servlets/purl/1645091.

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@article{osti_1645091,

  title        = {Enhancing easy-plane anisotropy in bespoke Ni(II) quantum magnets},

  author       = {Manson, Jamie L. and Manson, Zachary E. and Sargent, Ashley and Villa, Danielle Y. and Etten, Nicole L. and Blackmore, William J. A. and Curley, Samuel P. M. and Williams, Robert C. and Brambleby, Jamie and Goddard, Paul A. and Ozarowski, Andrew and Wilson, Murray N. and Huddart, Benjamin M. and Lancaster, Tom and Johnson, Roger D. and Blundell, Stephen J. and Bendix, Jesper and Wheeler, Kraig A. and Lapidus, Saul H. and Xiao, Fan and Birnbaum, Serena and Singleton, John},

  abstractNote = {We examine the crystal structures and magnetic properties of several S = 1 Ni(II) coordination compounds, molecules and polymers, that include the bridging ligands HF2-, AF62- (A = Ti, Zr) and pyrazine or non-bridging ligands F-, SiF62-, glycine, H2O, 1-vinylimidazole, 4-methylpyrazole and 3-hydroxypyridine. Pseudo-octahedral NiN4F2, NiN4O2 or NiN4OF cores consist of equatorial Ni-N bonds that are equal to or slightly longer than the axial Ni-Lax bonds. By design, the zero-field splitting (D) is large in these systems and, in the presence of substantial exchange interactions (J), can be difficult to discriminate from magnetometry measurements on powder samples. Thus, we relied on pulsed-field magnetization in those cases and employed electron-spin resonance (ESR) to confirm D when J ← D. The anisotropy of each compound was found to be easy-plane (D > 0) and range from ≈ 8–25 K. This work reveals a linear correlation between the ratio d(Ni-Lax)/d(Ni-Neq) and D although the ligand spectrochemical properties may play an important role. We assert that this relationship allows us to predict the type of magnetocrystalline anisotropy in tailored Ni(II) quantum magnets.},

  doi          = {10.1016/j.poly.2020.114379},

  journal      = {Polyhedron},

  number       = ,

  volume       = 180,

  place        = {United States},

  year         = {Wed Jan 22 00:00:00 EST 2020},

  month        = {Wed Jan 22 00:00:00 EST 2020}

}

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Title: Enhancing easy-plane anisotropy in bespoke Ni(II) quantum magnets

Abstract

Citation Formats

Multi-frequency, high-field EPR as a powerful tool to accurately determine zero-field splitting in high-spin transition metal coordination complexes journal, September 2006

Implications of bond disorder in a S=1 kagome lattice journal, March 2018

Controlling Magnetic Order and Quantum Disorder in Molecule-Based Magnets journal, May 2014

The Cambridge Structural Database journal, April 2016

Recent advances in magnetic structure determination by neutron powder diffraction journal, October 1993

Refinement of diaquabis(glycinato- O , N )nickel(II) journal, April 1982

Bimetallic MOFs (H 3 O) x [Cu(MF 6 )(pyrazine) 2 ]·(4 − x)H 2 O (M = V 4+ , x = 0; M = Ga 3+ , x = 1): co-existence of ordered and disordered quantum spins in the V 4+ system journal, January 2016

X-Seed — A Software Tool for Supramolecular Crystallography journal, July 2001

Valence bond description of antiferromagnetic coupling in transition metal dimers journal, May 1981

Beamline I11 at Diamond: A new instrument for high resolution powder diffraction journal, July 2009

Antiferromagnetism in a Family of S = 1 Square Lattice Coordination Polymers NiX 2 (pyz) 2 (X = Cl, Br, I, NCS; pyz = Pyrazine) journal, March 2016

Zero-field splitting in metal complexes journal, May 2004

SHELXT – Integrated space-group and crystal-structure determination journal, January 2015

Dimanganese catalase—spectroscopic parameters from broken-symmetry density functional theory of the superoxidized MnIII/MnIV state journal, April 2005

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal, January 2005

Experimental and Theoretical Electron Density Analysis of Copper Pyrazine Nitrate Quasi-Low-Dimensional Quantum Magnets journal, February 2016

Nonlinear Field Theory of Large-Spin Heisenberg Antiferromagnets: Semiclassically Quantized Solitons of the One-Dimensional Easy-Axis Néel State journal, April 1983

Experimentally determining the exchange parameters of quasi-two-dimensional Heisenberg magnets journal, August 2008

Thermodynamic and magnetic properties of the S =1 Heisenberg chain Ni( C 2 H 8 N 2 ) 2 Ni(CN ) 4 : Experiments and theory journal, August 1995

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

Characterizing the Haldane phase in quasi-one-dimensional spin-1 Heisenberg antiferromagnets journal, December 2014

Ab initio computations of effective exchange integrals for H–H, H–He–H and Mn2O2 complex: comparison of broken-symmetry approaches journal, March 2000

Strong H···F Hydrogen Bonds as Synthons in Polymeric Quantum Magnets: Structural, Magnetic, and Theoretical Characterization of [Cu(HF 2 )(pyrazine) 2 ]SbF 6 , [Cu 2 F(HF)(HF 2 )(pyrazine) 4 ](SbF 6 ) 2 , and [CuAg(H 3 F 4 )(pyrazine) 5 ](SbF 6 ) 2 journal, May 2009

Single-ion bound states in S = 1 Heisenberg antiferromagnetic chains with planar anisotropy and subcritical exchange coupling journal, August 1999

Spin-polarized muons in condensed matter physics journal, May 1999

Control of the third dimension in copper-based square-lattice antiferromagnets journal, March 2016

Crystal structure refinement with SHELXL journal, January 2015

Synthesis, structure, spectroscopy, and magnetism of transition-metal compounds with bridging hexafluorosilicate groups. Crystal and molecular structure of catena(-.mu.-hexafluorosilicato)tetrakis(N-vinylimidazole)cobalt(II) journal, October 1982

Quantum phase diagram and excitations for the one-dimensional S = 1 Heisenberg antiferromagnet with single-ion anisotropy journal, February 2009

Prediction of molecular properties and molecular spectroscopy with density functional theory: From fundamental theory to exchange-coupling journal, March 2009

Experiments on simple magnetic model systems journal, December 2001

Ordering, metastability and phase transitions in two-dimensional systems journal, April 1973

Structural, Electronic, and Magnetic Properties of Quasi-1D Quantum Magnets [Ni(HF 2 )(pyz) 2 ]X (pyz = pyrazine; X = PF 6 – , SbF 6 – ) Exhibiting Ni-FHF-Ni and Ni-pyz-Ni Spin Interactions journal, July 2011

Automatic Generation of Auxiliary Basis Sets journal, January 2017

Synthesis, Structures, Spectroscopy, and Magnetic Properties of Pyrazine-Bridged Two-Dimensional Complexes {Ni(pyz) 2 (OCN) 2 } n and {Ni(pyz) 2 (SCN) 2 } n journal, March 2010

Single crystal magnetic susceptibility measurements on the linear chain polymer copper (II) pyrazine nitrate journal, October 1973

Continuum dynamics of the 1-D Heisenberg antiferromagnet: Identification with the O(3) nonlinear sigma model journal, February 1983

Magnetic and thermodynamic properties of Ni ( C 10 H 8 N 2 ) 2 Ni ( CN ) 4 ⋅ H 2 O : A S = 1 Heisenberg antiferromagnetic chain with strong in-plane anisotropy and subcritical exchange coupling journal, February 2000

Ab-Initio Molecular Orbital Studies of Structure and Reactivity of Transition Metal-OXO Compounds book, January 1986

Characterization of a quasi-one-dimensional spin-1/2 magnet which is gapless and paramagnetic for g μ B H ≲ J and k B T ≪ J journal, January 1999

Determining the anisotropy and exchange parameters of polycrystalline spin-1 magnets journal, September 2019

Multi-frequency, high-field EPR as a powerful tool to accurately determine zero-field splitting in high-spin transition metal coordination complexes
journal, September 2006

Implications of bond disorder in a S=1 kagome lattice
journal, March 2018

Controlling Magnetic Order and Quantum Disorder in Molecule-Based Magnets
journal, May 2014

The Cambridge Structural Database
journal, April 2016

Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993

Refinement of diaquabis(glycinato- O , N )nickel(II)
journal, April 1982

Bimetallic MOFs (H ₃ O) _x [Cu(MF ₆ )(pyrazine) ₂ ]·(4 − x)H ₂ O (M = V ⁴⁺ , x = 0; M = Ga ³⁺ , x = 1): co-existence of ordered and disordered quantum spins in the V ⁴⁺ system
journal, January 2016

X-Seed — A Software Tool for Supramolecular Crystallography
journal, July 2001

Valence bond description of antiferromagnetic coupling in transition metal dimers
journal, May 1981

Beamline I11 at Diamond: A new instrument for high resolution powder diffraction
journal, July 2009

Antiferromagnetism in a Family of S = 1 Square Lattice Coordination Polymers NiX ₂ (pyz) ₂ (X = Cl, Br, I, NCS; pyz = Pyrazine)
journal, March 2016

Zero-field splitting in metal complexes
journal, May 2004

SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

Dimanganese catalase—spectroscopic parameters from broken-symmetry density functional theory of the superoxidized MnIII/MnIV state
journal, April 2005

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

Experimental and Theoretical Electron Density Analysis of Copper Pyrazine Nitrate Quasi-Low-Dimensional Quantum Magnets
journal, February 2016

Nonlinear Field Theory of Large-Spin Heisenberg Antiferromagnets: Semiclassically Quantized Solitons of the One-Dimensional Easy-Axis Néel State
journal, April 1983

Experimentally determining the exchange parameters of quasi-two-dimensional Heisenberg magnets
journal, August 2008

Thermodynamic and magnetic properties of the S =1 Heisenberg chain Ni( $C_{2}$ $H_{8}$ $N_{2}$ $)_{2}$ Ni(CN $)_{4}$ : Experiments and theory
journal, August 1995

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

Characterizing the Haldane phase in quasi-one-dimensional spin-1 Heisenberg antiferromagnets
journal, December 2014

Ab initio computations of effective exchange integrals for H–H, H–He–H and Mn2O2 complex: comparison of broken-symmetry approaches
journal, March 2000

Strong H···F Hydrogen Bonds as Synthons in Polymeric Quantum Magnets: Structural, Magnetic, and Theoretical Characterization of [Cu(HF ₂ )(pyrazine) ₂ ]SbF ₆ , [Cu ₂ F(HF)(HF ₂ )(pyrazine) ₄ ](SbF ₆ ) ₂ , and [CuAg(H ₃ F ₄ )(pyrazine) ₅ ](SbF ₆ ) ₂
journal, May 2009

Single-ion bound states in $S = 1$ Heisenberg antiferromagnetic chains with planar anisotropy and subcritical exchange coupling
journal, August 1999

Spin-polarized muons in condensed matter physics
journal, May 1999

Control of the third dimension in copper-based square-lattice antiferromagnets
journal, March 2016

Crystal structure refinement with SHELXL
journal, January 2015

Synthesis, structure, spectroscopy, and magnetism of transition-metal compounds with bridging hexafluorosilicate groups. Crystal and molecular structure of catena(-.mu.-hexafluorosilicato)tetrakis(N-vinylimidazole)cobalt(II)
journal, October 1982

Quantum phase diagram and excitations for the one-dimensional $S = 1$ Heisenberg antiferromagnet with single-ion anisotropy
journal, February 2009

Prediction of molecular properties and molecular spectroscopy with density functional theory: From fundamental theory to exchange-coupling
journal, March 2009

Experiments on simple magnetic model systems
journal, December 2001

Ordering, metastability and phase transitions in two-dimensional systems
journal, April 1973

Structural, Electronic, and Magnetic Properties of Quasi-1D Quantum Magnets [Ni(HF ₂ )(pyz) ₂ ]X (pyz = pyrazine; X = PF ₆ ^– , SbF ₆ ^– ) Exhibiting Ni-FHF-Ni and Ni-pyz-Ni Spin Interactions
journal, July 2011

Automatic Generation of Auxiliary Basis Sets
journal, January 2017

Synthesis, Structures, Spectroscopy, and Magnetic Properties of Pyrazine-Bridged Two-Dimensional Complexes {Ni(pyz) ₂ (OCN) ₂ } _n and {Ni(pyz) ₂ (SCN) ₂ } _n
journal, March 2010

Single crystal magnetic susceptibility measurements on the linear chain polymer copper (II) pyrazine nitrate
journal, October 1973

Continuum dynamics of the 1-D Heisenberg antiferromagnet: Identification with the O(3) nonlinear sigma model
journal, February 1983

Magnetic and thermodynamic properties of $Ni (C_{10} H_{8} N_{2})_{2} {Ni (CN)}_{4} \cdot H_{2} O :$ A $S = 1$ Heisenberg antiferromagnetic chain with strong in-plane anisotropy and subcritical exchange coupling
journal, February 2000

Ab-Initio Molecular Orbital Studies of Structure and Reactivity of Transition Metal-OXO Compounds
book, January 1986

Characterization of a quasi-one-dimensional spin-1/2 magnet which is gapless and paramagnetic for $g μ_{B} H ≲ J$ and $k_{B} T ≪ J$
journal, January 1999

Determining the anisotropy and exchange parameters of polycrystalline spin-1 magnets
journal, September 2019