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Title: Long-range magnetic order in Mn[N(CN)2]2(pyz) {pyz = pyrazine}. susceptibility, magnetization, specific heat and neutron diffraction measurements and electronic structure calculations.

Abstract

Using dc magnetization, ac susceptibility, specific heat, and neutron diffraction, we have studied the magnetic properties of Mn[N(CN){sub 2}]{sub 2}(pyz) (pyz = pyrazine) in detail. The material crystallizes in the monoclinic space group P2{sub 1}/n with a = 7.3248(2), b = 16.7369(4), and c = 8.7905(2) {angstrom}, {beta} = 89.596(2){sup o}, V = 1077.65(7) {angstrom}{sup 3}, and Z = 4, as determined by Rietveld refinement of neutron powder diffraction data at 1.35 K. The 5 K neutron powder diffraction data reflect very little variation in the crystal structure. Interpenetrating ReO{sub 3}-like networks are formed from axially elongated Mn{sup 2+} octahedra and edges made up of {mu}-bonded [N(CN){sub 2}]{sup -} anions and neutral pyz ligands. A three-dimensional antiferromagnetic ordering occurs below T{sub N} = 2.53(2) k. The magnetic unit cell is double the nuclear one along the a- and c-axes, giving the (1/2, 0, 1/2) superstructure. The crystallographic and antiferromagnetic structures are commensurate and consist of collinear Mn{sup 2+} moments, each with a magnitude of 4.15(6) {mu}{sub B} aligned parallel to the a-direction (Mn-pyz-Mn chains). Electronic structure calculations indicate that the exchange interaction is much stronger along the Mn-pyz-Mn chain axis than along the Mn-NCNCN-Mn axes by a factor of approximatelymore » 40, giving rise to a predominantly one-dimensional magnetic system. Thus, the variable-temperature magnetic susceptibility data are well described by a Heisenberg antiferromagnetic chain model, giving g = 2.01(1) and J/k{sub B} = -0.27(1) K. Owing to single-ion anisotropy of the Mn{sup 2+} ion, field-induced phenomena ascribed to spin-flop and paramagnetic transitions are observed at 0.43 and 2.83 T, respectively.« less

Authors:
; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
942979
Report Number(s):
ANL/CHM/JA-36448
Journal ID: ISSN 0002-7863; JACSAT; TRN: US201002%%479
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.
Additional Journal Information:
Journal Volume: 123; Journal Issue: Jan. 10, 2001; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE; ANIONS; ANISOTROPY; CRYSTAL STRUCTURE; DIFFRACTION; ELECTRONIC STRUCTURE; EXCHANGE INTERACTIONS; LIGANDS; MAGNETIC PROPERTIES; MAGNETIC SUSCEPTIBILITY; MAGNETIZATION; MATERIALS; NEUTRON DIFFRACTION; NEUTRONS; POWDERS; SPACE GROUPS; SPECIFIC HEAT; VARIATIONS

Citation Formats

Manson, J L, Huang, Q -Z, Lynn, J W, Koo, H -J, Whangbo, M -H, Bateman, R, Wada, N, Awaga, K, Argyriou, D N, Miller, J S, Univ. of Maryland, National Inst. of Standards & Technology, North Carolina State Univ., Oxford Research Instruments, Univ. of Tokyo, and Univ. of Utah. Long-range magnetic order in Mn[N(CN)2]2(pyz) {pyz = pyrazine}. susceptibility, magnetization, specific heat and neutron diffraction measurements and electronic structure calculations.. United States: N. p., 2001. Web. doi:10.1021/ja0024791.
Manson, J L, Huang, Q -Z, Lynn, J W, Koo, H -J, Whangbo, M -H, Bateman, R, Wada, N, Awaga, K, Argyriou, D N, Miller, J S, Univ. of Maryland, National Inst. of Standards & Technology, North Carolina State Univ., Oxford Research Instruments, Univ. of Tokyo, & Univ. of Utah. Long-range magnetic order in Mn[N(CN)2]2(pyz) {pyz = pyrazine}. susceptibility, magnetization, specific heat and neutron diffraction measurements and electronic structure calculations.. United States. https://doi.org/10.1021/ja0024791
Manson, J L, Huang, Q -Z, Lynn, J W, Koo, H -J, Whangbo, M -H, Bateman, R, Wada, N, Awaga, K, Argyriou, D N, Miller, J S, Univ. of Maryland, National Inst. of Standards & Technology, North Carolina State Univ., Oxford Research Instruments, Univ. of Tokyo, and Univ. of Utah. Wed . "Long-range magnetic order in Mn[N(CN)2]2(pyz) {pyz = pyrazine}. susceptibility, magnetization, specific heat and neutron diffraction measurements and electronic structure calculations.". United States. https://doi.org/10.1021/ja0024791.
@article{osti_942979,
title = {Long-range magnetic order in Mn[N(CN)2]2(pyz) {pyz = pyrazine}. susceptibility, magnetization, specific heat and neutron diffraction measurements and electronic structure calculations.},
author = {Manson, J L and Huang, Q -Z and Lynn, J W and Koo, H -J and Whangbo, M -H and Bateman, R and Wada, N and Awaga, K and Argyriou, D N and Miller, J S and Univ. of Maryland and National Inst. of Standards & Technology and North Carolina State Univ. and Oxford Research Instruments and Univ. of Tokyo and Univ. of Utah},
abstractNote = {Using dc magnetization, ac susceptibility, specific heat, and neutron diffraction, we have studied the magnetic properties of Mn[N(CN){sub 2}]{sub 2}(pyz) (pyz = pyrazine) in detail. The material crystallizes in the monoclinic space group P2{sub 1}/n with a = 7.3248(2), b = 16.7369(4), and c = 8.7905(2) {angstrom}, {beta} = 89.596(2){sup o}, V = 1077.65(7) {angstrom}{sup 3}, and Z = 4, as determined by Rietveld refinement of neutron powder diffraction data at 1.35 K. The 5 K neutron powder diffraction data reflect very little variation in the crystal structure. Interpenetrating ReO{sub 3}-like networks are formed from axially elongated Mn{sup 2+} octahedra and edges made up of {mu}-bonded [N(CN){sub 2}]{sup -} anions and neutral pyz ligands. A three-dimensional antiferromagnetic ordering occurs below T{sub N} = 2.53(2) k. The magnetic unit cell is double the nuclear one along the a- and c-axes, giving the (1/2, 0, 1/2) superstructure. The crystallographic and antiferromagnetic structures are commensurate and consist of collinear Mn{sup 2+} moments, each with a magnitude of 4.15(6) {mu}{sub B} aligned parallel to the a-direction (Mn-pyz-Mn chains). Electronic structure calculations indicate that the exchange interaction is much stronger along the Mn-pyz-Mn chain axis than along the Mn-NCNCN-Mn axes by a factor of approximately 40, giving rise to a predominantly one-dimensional magnetic system. Thus, the variable-temperature magnetic susceptibility data are well described by a Heisenberg antiferromagnetic chain model, giving g = 2.01(1) and J/k{sub B} = -0.27(1) K. Owing to single-ion anisotropy of the Mn{sup 2+} ion, field-induced phenomena ascribed to spin-flop and paramagnetic transitions are observed at 0.43 and 2.83 T, respectively.},
doi = {10.1021/ja0024791},
url = {https://www.osti.gov/biblio/942979}, journal = {J. Am. Chem. Soc.},
issn = {0002-7863},
number = Jan. 10, 2001,
volume = 123,
place = {United States},
year = {2001},
month = {1}
}