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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.

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

Authors :
Murashima K
Watanabe T
Kanegawa S
Yoshihara D
Inagaki Y
Karasawa S
Koga N
Source :
Inorganic chemistry [Inorg Chem] 2012 May 07; Vol. 51 (9), pp. 4982-93. Date of Electronic Publication: 2012 Apr 10.
Publication Year :
2012

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.

Details

Language :
English
ISSN :
1520-510X
Volume :
51
Issue :
9
Database :
MEDLINE
Journal :
Inorganic chemistry
Publication Type :
Academic Journal
Accession number :
22490003
Full Text :
https://doi.org/10.1021/ic202397m