Preparations, crystal structures, and magnetic properties of N, N-dipyridylaminoxyl as a new magnetic coupler and its one-dimensional cobalt(II) chains

Kensuke Murashima, Takeaki Watanabe, Shinji Kanegawa, Daisuke Yoshihara, Yuji Inagaki, Satoru Karasawa, Noboru Koga

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Abstract

N,N-Dipyridilaminoxyl, NOpy 2, having a stable aminoxyl, was prepared as a new magnetic coupler for heterospin systems. Solutions of NOpy 2 were mixed with those of bis{1,1,1,5,5,5, hexafluoro-4- (phenylimino)-2-pentanonate}cobalt derivatives, Co(hfpip-X) 2, at a 1:1 ratio to afford the polymeric cobalt(II) complexes, [Co(hfpip-X) 2(NOpy 2)] n; X = H (1), F (2), F 3 (3), F 5 (4), Cl (5), Cl 3 (6), Br (7), and I (8) as single crystals. In all complexes, the local structures of the cobalt-complex units were compressed octahedra and the pyridine ligands in NOpy 2 units coordinated to the cobalt ions in trans configuration to form linear chains for 1-4 and in cis configuration to form helical chains for 5-8. In the chains, the aminoxyl in NOpy 2 ferromagnetically interacted with the cobalt ions to produce the ferromagnetic chains with J intra/k B = 9-14 K. In the magnetic susceptibility experiments of aligned sample of 6, the magnetic easy axis was determined to be the a* axis, which was the direction perpendicular to the b axis of the chain axis. The resulting chains, all except 4, interacted antiferromagnetically among each other, and especially in 1, 5, 7, and 8, the magnetic behaviors characteristic to canted two-dimensional (2D) antiferromagnets with T c = 5.6, 4.0, 4.0, and 6.2 K, respectively, were observed. All complexes showed slow magnetic relaxations affected by the interchain antiferromagnetic interaction. The effective activation barriers, Δ eff/k B, for the reorientation of the magnetism for all complexes except 4 were estimated to be 25-39 K in the presence of a direct current (dc) field.

Original languageEnglish
Pages (from-to)4982-4993
Number of pages12
JournalInorganic chemistry
Volume51
Issue number9
DOIs
Publication statusPublished - May 7 2012

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Cobalt
couplers
Magnetic properties
cobalt
Crystal structure
magnetic properties
preparation
crystal structure
Ions
Magnetic relaxation
Magnetism
Magnetic susceptibility
magnetic relaxation
configurations
retraining
Chemical activation
Single crystals
pyridines
ions
Ligands

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Preparations, crystal structures, and magnetic properties of N, N-dipyridylaminoxyl as a new magnetic coupler and its one-dimensional cobalt(II) chains. / Murashima, Kensuke; Watanabe, Takeaki; Kanegawa, Shinji; Yoshihara, Daisuke; Inagaki, Yuji; Karasawa, Satoru; Koga, Noboru.

In: Inorganic chemistry, Vol. 51, No. 9, 07.05.2012, p. 4982-4993.

Research output: Contribution to journalArticle

Murashima, Kensuke ; Watanabe, Takeaki ; Kanegawa, Shinji ; Yoshihara, Daisuke ; Inagaki, Yuji ; Karasawa, Satoru ; Koga, Noboru. / Preparations, crystal structures, and magnetic properties of N, N-dipyridylaminoxyl as a new magnetic coupler and its one-dimensional cobalt(II) chains. In: Inorganic chemistry. 2012 ; Vol. 51, No. 9. pp. 4982-4993.
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abstract = "N,N-Dipyridilaminoxyl, NOpy 2, having a stable aminoxyl, was prepared as a new magnetic coupler for heterospin systems. Solutions of NOpy 2 were mixed with those of bis{1,1,1,5,5,5, hexafluoro-4- (phenylimino)-2-pentanonate}cobalt derivatives, Co(hfpip-X) 2, at a 1:1 ratio to afford the polymeric cobalt(II) complexes, [Co(hfpip-X) 2(NOpy 2)] n; X = H (1), F (2), F 3 (3), F 5 (4), Cl (5), Cl 3 (6), Br (7), and I (8) as single crystals. In all complexes, the local structures of the cobalt-complex units were compressed octahedra and the pyridine ligands in NOpy 2 units coordinated to the cobalt ions in trans configuration to form linear chains for 1-4 and in cis configuration to form helical chains for 5-8. In the chains, the aminoxyl in NOpy 2 ferromagnetically interacted with the cobalt ions to produce the ferromagnetic chains with J intra/k B = 9-14 K. In the magnetic susceptibility experiments of aligned sample of 6, the magnetic easy axis was determined to be the a* axis, which was the direction perpendicular to the b axis of the chain axis. The resulting chains, all except 4, interacted antiferromagnetically among each other, and especially in 1, 5, 7, and 8, the magnetic behaviors characteristic to canted two-dimensional (2D) antiferromagnets with T c = 5.6, 4.0, 4.0, and 6.2 K, respectively, were observed. All complexes showed slow magnetic relaxations affected by the interchain antiferromagnetic interaction. The effective activation barriers, Δ eff/k B, for the reorientation of the magnetism for all complexes except 4 were estimated to be 25-39 K in the presence of a direct current (dc) field.",
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T1 - Preparations, crystal structures, and magnetic properties of N, N-dipyridylaminoxyl as a new magnetic coupler and its one-dimensional cobalt(II) chains

AU - Murashima, Kensuke

AU - Watanabe, Takeaki

AU - Kanegawa, Shinji

AU - Yoshihara, Daisuke

AU - Inagaki, Yuji

AU - Karasawa, Satoru

AU - Koga, Noboru

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AB - N,N-Dipyridilaminoxyl, NOpy 2, having a stable aminoxyl, was prepared as a new magnetic coupler for heterospin systems. Solutions of NOpy 2 were mixed with those of bis{1,1,1,5,5,5, hexafluoro-4- (phenylimino)-2-pentanonate}cobalt derivatives, Co(hfpip-X) 2, at a 1:1 ratio to afford the polymeric cobalt(II) complexes, [Co(hfpip-X) 2(NOpy 2)] n; X = H (1), F (2), F 3 (3), F 5 (4), Cl (5), Cl 3 (6), Br (7), and I (8) as single crystals. In all complexes, the local structures of the cobalt-complex units were compressed octahedra and the pyridine ligands in NOpy 2 units coordinated to the cobalt ions in trans configuration to form linear chains for 1-4 and in cis configuration to form helical chains for 5-8. In the chains, the aminoxyl in NOpy 2 ferromagnetically interacted with the cobalt ions to produce the ferromagnetic chains with J intra/k B = 9-14 K. In the magnetic susceptibility experiments of aligned sample of 6, the magnetic easy axis was determined to be the a* axis, which was the direction perpendicular to the b axis of the chain axis. The resulting chains, all except 4, interacted antiferromagnetically among each other, and especially in 1, 5, 7, and 8, the magnetic behaviors characteristic to canted two-dimensional (2D) antiferromagnets with T c = 5.6, 4.0, 4.0, and 6.2 K, respectively, were observed. All complexes showed slow magnetic relaxations affected by the interchain antiferromagnetic interaction. The effective activation barriers, Δ eff/k B, for the reorientation of the magnetism for all complexes except 4 were estimated to be 25-39 K in the presence of a direct current (dc) field.

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