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水合苯甲酸钴(ii)中异常缓慢的磁弛豫。

Exceptionally slow magnetic relaxation in cobalt(ii) benzoate trihydrate.

机构信息

Department of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University in Košice, 041 54 Košice, Slovakia.

Department of Chemistry, Faculty of Natural Sciences, University of SS. Cyril and Methodius, 91701 Trnava, Slovakia.

出版信息

Dalton Trans. 2018 Nov 21;47(43):15523-15529. doi: 10.1039/c8dt03610a. Epub 2018 Oct 19.

Abstract

Cobalt(ii) benzoate trihydrate prepared by the reaction of CoCO with benzoic acid (HBz) in boiling water followed by crystallization has been structurally characterized as a chain-like system with the formula unit [Co(Bz)(HO)]Bz·HO where the Co(ii) atoms are triply linked by one bridging syn-syn benzoato (Bz) and two aqua ligands; additional benzoate counter ions and solvate water molecules are present in the crystal structure. DC magnetic measurements reveal a sizable exchange coupling of a ferromagnetic nature between the Co(ii) atoms. At T = 5.5 K the paramagnetic phase switches to the antiferromagnetic phase. Though the remnant magnetization is zero, the magnetization curve shows two lobes of a hysteresis loop and the DC relaxation experiments confirm a long relaxation time at T = 2.0 K. AC susceptibility data confirm a slow relaxation of magnetization even in the antiferromagnetic phase. In the absence of the magnetic field, two relaxation channels exist. The relaxation time for the low frequency channel is as slow as τ > 1.6 s and data fitting yields τ (2.1 K) = 14 s. The high-frequency relaxation time obeys the Orbach process at a higher temperature whereas the Raman process dominates the low-temperature region. Three slow relaxation channels are evidenced at the applied magnetic field B = 0.1 T.

摘要

水热条件下 CoCO3 与苯甲酸(HBz)反应得到的二水合苯甲酸钴(II)已被结构确证为具有链状结构的化合物,其分子式单元为[Co(Bz)(HO)]Bz·HO,其中 Co(II)原子通过一个桥联的顺式-顺式苯甲酸根(Bz)和两个水分子连接,此外,晶体结构中还存在额外的苯甲酸根抗衡离子和溶剂水分子。直流磁测量结果表明,Co(II)原子之间存在铁磁性质的可观的交换耦合。在 T = 5.5 K 时,顺磁相转变为反铁磁相。尽管剩余磁化强度为零,但磁化曲线显示出两个磁滞回线的磁滞回线瓣,直流弛豫实验证实了在 T = 2.0 K 时弛豫时间较长。交流磁化率数据证实了即使在反铁磁相中磁化率的缓慢弛豫。在没有磁场的情况下,存在两个弛豫通道。低频通道的弛豫时间非常缓慢,τ > 1.6 s,数据拟合得到 τ(2.1 K)= 14 s。在较高温度下,高频弛豫时间遵循 Orbach 过程,而在低温区域则由 Raman 过程主导。在施加磁场 B = 0.1 T 的情况下,证明了三个缓慢弛豫通道的存在。

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