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由钴(II)离子和手性三重态双(氮氧化物)自由基组成的分子基磁体中的场致亚铁磁态。

Field-induced ferrimagnetic state in a molecule-based magnet consisting of a Co(II) ion and a chiral triplet Bis(nitroxide) radical.

作者信息

Numata Youhei, Inoue Katsuya, Baranov Nikolai, Kurmoo Mohamedally, Kikuchi Koichi

机构信息

Department of Structural Molecular Science, The Graduate University for Advanced Studies, Okazaki 444-8585, Japan.

出版信息

J Am Chem Soc. 2007 Aug 15;129(32):9902-9. doi: 10.1021/ja064828i. Epub 2007 Jul 21.

Abstract

We present the synthesis, crystal structure, and temperature and field dependence of the magnetic properties of a new molecule-based magnet, [Co(hfac)2].BNO* (1), where hfac = 1,1,1,5,5,5-hexafluoroacetylacetonato and BNO* is the chiral triplet bis(nitroxide), 1,3-bis(N-tert-butyl-N-oxylamino)-5-{1'-methyl-1'-[2' '-(S)-methylbutoxy]ethyl}benzene. The presence of enantiomer-pure BNO induces the formation of chiral one-dimensional chains that are packed parallel to each other in the noncentrosymmetric P1 space group. 1 exhibits four magnetic ground states: paramagnetic; antiferromagnetic; forced ferrimagnetic; field-induced metastable ferrimagnetic. In the paramagnetic state (T > 20 K), it presents short-range antiferromagnetic interaction between Co ion and nitroxide radical and has a minimum of chimT value at 220 K. The Weiss temperature estimated in the temperature range 220-300 K is found to be -89.9 K. At 20 K (TN), an antiferromagnetic long-range ordering is established. In the temperature range 4 K < T < 20 K, the isothermal magnetization curve show a spin-flip transition to the forced ferrimagnetic state at around 850 Oe. Below 4 K, this compound enters into a field-induced ferrimagnetic state, which is metastable and stabilized by the Ising character of the Co ion. In the low-temperature phase, the material becomes a very hard magnet with wide hysteresis loop whose coercive field reaches 25 kOe at 2 K. The magnetic phase diagram based on these magnetic data is presented.

摘要

我们报道了一种新型分子基磁体[Co(hfac)₂]·BNO* (1)的合成、晶体结构以及磁性能的温度和磁场依赖性,其中hfac = 1,1,1,5,5,5 - 六氟乙酰丙酮,BNO*是手性三重态双(氮氧化物),即1,3 - 双(N - 叔丁基 - N - 氧基氨基)-5 - {1'-甲基 - 1'-[2''-(S)-甲基丁氧基]乙基}苯。对映体纯的BNO的存在诱导形成了手性一维链,这些链在非中心对称的P1空间群中相互平行排列。1呈现出四种磁基态:顺磁态;反铁磁态;强制亚铁磁态;场诱导亚稳亚铁磁态。在顺磁态(T > 20 K)下,它在钴离子和氮氧化物自由基之间呈现短程反铁磁相互作用,并且在220 K时具有最小的χmT值。在220 - 300 K温度范围内估计的魏斯温度为 - 89.9 K。在20 K(TN)时,建立了反铁磁长程有序。在4 K < T < 20 K温度范围内,等温磁化曲线在约850 Oe处显示自旋翻转转变为强制亚铁磁态。在4 K以下,该化合物进入场诱导亚铁磁态,该状态是亚稳的,并由钴离子的伊辛特性稳定。在低温相中,该材料成为具有宽磁滞回线的非常硬的磁体,其矫顽场在2 K时达到25 kOe。基于这些磁数据给出了磁相图。

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