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在具有负轴向分量的三轴各向异性的顺式-[Co(hfac)(HO)]中,场诱导慢磁弛豫的证据。

Evidence of field induced slow magnetic relaxation in cis-[Co(hfac)(HO)] exhibiting tri-axial anisotropy with a negative axial component.

作者信息

Korchagin Denis V, Palii Andrew V, Yureva Elena A, Akimov Alexander V, Misochko Eugenii Ya, Shilov Gennady V, Talantsev Artem D, Morgunov Roman B, Shakin Alexander A, Aldoshin Sergey M, Tsukerblat Boris S

机构信息

Institute of Problems of Chemical Physics, Chernogolovka, Moscow Region, Russia.

出版信息

Dalton Trans. 2017 Jun 13;46(23):7540-7548. doi: 10.1039/c7dt01236e.

Abstract

We report a combined experimental characterization and theoretical modeling of the hexa-coordinated high-spin Co(ii) complex cis-[Co(hfac)(HO)] (I). The magnetic static field (DC) data and EPR spectra (measurements were carried out on the powder samples of diluted samples cis-[CoZn (hfac)(HO)]) were analyzed with the aid of the parametric Griffith Hamiltonian for the high-spin Co(ii) supported by the ab initio calculations of the crystal field (CF) parameters, g-factors and superexchange parameters between H-bonded Co(ii) ions in the neighboring molecules in a 1D network. This analysis suggests the presence of the easy axis of magnetic anisotropy and also shows the existence of a significant rhombic component. The detected frequency dependent (AC) susceptibility signal shows that complex I exhibits slow paramagnetic relaxation in the applied DC field belonging thus to the class of non-uniaxial field induced single ion magnets with a negative axial component of anisotropy. It is demonstrated that the main contributions to the relaxation come from the direct one-phonon process dominating at low temperatures, while the contribution of the two-phonon Raman process becomes important with increasing temperature.

摘要

我们报告了六配位高自旋Co(ii)配合物顺式-[Co(hfac)(HO)] (I)的实验表征与理论建模相结合的研究。借助于由晶体场(CF)参数、g因子以及一维网络中相邻分子间氢键合的Co(ii)离子之间的超交换参数的从头算所支持的高自旋Co(ii)的参数化格里菲斯哈密顿量,对静磁场(DC)数据和EPR光谱(对稀释样品顺式-[CoZn (hfac)(HO)]的粉末样品进行测量)进行了分析。该分析表明存在磁各向异性的易轴,并且还显示出存在显著的菱形分量。检测到的频率相关(AC)磁化率信号表明,配合物I在所施加的直流场中表现出缓慢的顺磁弛豫,因此属于具有负各向异性轴向分量的非单轴场诱导单离子磁体类别。结果表明,弛豫的主要贡献来自于低温下主导的直接单声子过程,而随着温度升高,两声子拉曼过程的贡献变得重要。

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