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

Title: Structural Electronic and Magnetic Properties of Quasi-1D Quantum Magnets [Ni(HF2)(pyz)2]X (pyz = pyrazine; X = PF6- SbF6-) Exhibiting Ni-FHF-Ni and Ni-pyz-Ni Spin Interactions

Abstract

[Ni(HF{sub 2})(pyz){sub 2}]X {l_brace}pyz = pyrazine; X = PF{sub 6}{sup -} (1), SbF{sub 6}{sup -} (2){r_brace} were structurally characterized by synchrotron X-ray powder diffraction and found to possess axially compressed NiN{sub 4}F{sub 2} octahedra. At 298 K, 1 is monoclinic (C2/c) with unit cell parameters, a = 9.9481(3), b = 9.9421(3), c = 12.5953(4) {angstrom}, and {beta} = 81.610(3){sup o} while 2 is tetragonal (P4/nmm) with a = b = 9.9359(3) and c = 6.4471(2) {angstrom} and is isomorphic with the Cu-analogue. Infinite one-dimensional (1D) Ni-FHF-Ni chains propagate along the c-axis which are linked via {mu}-pyz bridges in the ab-plane to afford three-dimensional polymeric frameworks with PF{sub 6}{sup -} and SbF{sub 6}{sup -} counterions occupying the interior sites. A major difference between 1 and 2 is that the Ni-F-H bonds are bent (157{sup o}) in 1 but are linear in 2. Ligand field calculations (LFT) based on an angular overlap model (AOM), with comparison to the electronic absorption spectra, indicate greater {pi}-donation of the HF{sub 2}{sup -} ligand in 1 owing to the bent Ni-F-H bonds. Magnetic susceptibility data for 1 and 2 exhibit broad maxima at 7.4 and 15 K, respectively, and {lambda}-like peaks in dxT/dT at 6.2 andmore » 12.2 K that are ascribed to transitions to long-range antiferromagnetic order (TN). Muon-spin relaxation and specific heat studies confirm these TN's. A comparative analysis of x vs T to various 1D Heisenberg/Ising models suggests moderate antiferromagnetic interactions, with the primary interaction strength determined to be 3.05/3.42 K (1) and 5.65/6.37 K (2). However, high critical fields of 19 and 37.4 T obtained from low temperature pulsed-field magnetization data indicate that a single exchange constant (J1D) alone is insufficient to explain the data and that residual terms in the spin Hamiltonian, which could include interchain magnetic couplings (J), as mediated by Ni-pyz-Ni, and single-ion anisotropy (D), must be considered. While it is difficult to draw absolute conclusions regarding the magnitude (and sign) of J and D based solely on powder data, further support offered by related Ni(II)-pyz compounds and our LFT and density-functional theory (DFT) results lead us to a consistent quasi-1D magnetic description for 1 and 2.« less

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE SC OFFICE OF SCIENCE (SC)
OSTI Identifier:
1041979
Report Number(s):
BNL-97657-2012-JA
Journal ID: ISSN 0020-1669; INOCAJ; TRN: US201212%%390
DOE Contract Number:  
DE-AC02-98CH10886
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 50; Journal Issue: 13; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; ANISOTROPY; CRITICAL FIELD; DIFFRACTION; MAGNETIC PROPERTIES; MAGNETIC SUSCEPTIBILITY; MAGNETIZATION; MAGNETS; RELAXATION; SPECIFIC HEAT; SPIN; SYNCHROTRONS

Citation Formats

Manson, J, Lapidus, S, Stephens, P, Peterson, P, Carreiro, K, Southerland, H, Lancaster, T, Blundell, S, Steele, A, and et al. Structural Electronic and Magnetic Properties of Quasi-1D Quantum Magnets [Ni(HF2)(pyz)2]X (pyz = pyrazine; X = PF6- SbF6-) Exhibiting Ni-FHF-Ni and Ni-pyz-Ni Spin Interactions. United States: N. p., 2011. Web. doi:10.1021/ic102532h.
Manson, J, Lapidus, S, Stephens, P, Peterson, P, Carreiro, K, Southerland, H, Lancaster, T, Blundell, S, Steele, A, & et al. Structural Electronic and Magnetic Properties of Quasi-1D Quantum Magnets [Ni(HF2)(pyz)2]X (pyz = pyrazine; X = PF6- SbF6-) Exhibiting Ni-FHF-Ni and Ni-pyz-Ni Spin Interactions. United States. doi:10.1021/ic102532h.
Manson, J, Lapidus, S, Stephens, P, Peterson, P, Carreiro, K, Southerland, H, Lancaster, T, Blundell, S, Steele, A, and et al. Sat . "Structural Electronic and Magnetic Properties of Quasi-1D Quantum Magnets [Ni(HF2)(pyz)2]X (pyz = pyrazine; X = PF6- SbF6-) Exhibiting Ni-FHF-Ni and Ni-pyz-Ni Spin Interactions". United States. doi:10.1021/ic102532h.
@article{osti_1041979,
title = {Structural Electronic and Magnetic Properties of Quasi-1D Quantum Magnets [Ni(HF2)(pyz)2]X (pyz = pyrazine; X = PF6- SbF6-) Exhibiting Ni-FHF-Ni and Ni-pyz-Ni Spin Interactions},
author = {Manson, J and Lapidus, S and Stephens, P and Peterson, P and Carreiro, K and Southerland, H and Lancaster, T and Blundell, S and Steele, A and et al.},
abstractNote = {[Ni(HF{sub 2})(pyz){sub 2}]X {l_brace}pyz = pyrazine; X = PF{sub 6}{sup -} (1), SbF{sub 6}{sup -} (2){r_brace} were structurally characterized by synchrotron X-ray powder diffraction and found to possess axially compressed NiN{sub 4}F{sub 2} octahedra. At 298 K, 1 is monoclinic (C2/c) with unit cell parameters, a = 9.9481(3), b = 9.9421(3), c = 12.5953(4) {angstrom}, and {beta} = 81.610(3){sup o} while 2 is tetragonal (P4/nmm) with a = b = 9.9359(3) and c = 6.4471(2) {angstrom} and is isomorphic with the Cu-analogue. Infinite one-dimensional (1D) Ni-FHF-Ni chains propagate along the c-axis which are linked via {mu}-pyz bridges in the ab-plane to afford three-dimensional polymeric frameworks with PF{sub 6}{sup -} and SbF{sub 6}{sup -} counterions occupying the interior sites. A major difference between 1 and 2 is that the Ni-F-H bonds are bent (157{sup o}) in 1 but are linear in 2. Ligand field calculations (LFT) based on an angular overlap model (AOM), with comparison to the electronic absorption spectra, indicate greater {pi}-donation of the HF{sub 2}{sup -} ligand in 1 owing to the bent Ni-F-H bonds. Magnetic susceptibility data for 1 and 2 exhibit broad maxima at 7.4 and 15 K, respectively, and {lambda}-like peaks in dxT/dT at 6.2 and 12.2 K that are ascribed to transitions to long-range antiferromagnetic order (TN). Muon-spin relaxation and specific heat studies confirm these TN's. A comparative analysis of x vs T to various 1D Heisenberg/Ising models suggests moderate antiferromagnetic interactions, with the primary interaction strength determined to be 3.05/3.42 K (1) and 5.65/6.37 K (2). However, high critical fields of 19 and 37.4 T obtained from low temperature pulsed-field magnetization data indicate that a single exchange constant (J1D) alone is insufficient to explain the data and that residual terms in the spin Hamiltonian, which could include interchain magnetic couplings (J), as mediated by Ni-pyz-Ni, and single-ion anisotropy (D), must be considered. While it is difficult to draw absolute conclusions regarding the magnitude (and sign) of J and D based solely on powder data, further support offered by related Ni(II)-pyz compounds and our LFT and density-functional theory (DFT) results lead us to a consistent quasi-1D magnetic description for 1 and 2.},
doi = {10.1021/ic102532h},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 13,
volume = 50,
place = {United States},
year = {2011},
month = {12}
}