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f-f相互作用对磁化量子隧穿的影响:具有相同八配位环境的单核和双核酞菁基镝(III)三层单分子磁体

Effect of f-f interactions on quantum tunnelling of the magnetization: mono- and dinuclear Dy(III) phthalocyaninato triple-decker single-molecule magnets with the same octacoordination environment.

作者信息

Katoh Keiichi, Asano Rina, Miura Akira, Horii Yoji, Morita Takaumi, Breedlove Brian K, Yamashita Masahiro

机构信息

Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, Sendai, Miyagi 980-8578, Japan.

出版信息

Dalton Trans. 2014 Jun 7;43(21):7716-25. doi: 10.1039/c4dt00042k. Epub 2014 Mar 7.

Abstract

The single-molecule magnet (SMM) behaviour of dinuclear Ln(III)-Pc triple-decker complexes (Dy(III)-Y(III): 1 and Dy(III)-Dy(III): 2) with the same octacoordination environment and slow magnetic relaxation behaviour were explained using X-ray crystallography and static and dynamic susceptibility measurements. In particular, interactions among the 4f electrons of dinuclear Dy(III)-Pc triple-decker type SMMs have never been discussed on the basis of the same octacoordination environment. Our results clearly show that the Dy(III) ion sites of 1 and 2 are equivalent, consistent with the crystal structure. 2 Exhibited ferromagnetic interaction between Dy(III) ions. This is clear evidence that the magnetic relaxation mechanism depends heavily on the dipole-dipole (f-f) interactions between the Dy(III) ions in the dinuclear systems. For both 1 and 2, quantum tunnelling of the magnetization (QTM) was observed. However, the magnetic relaxation time (τ) for 2 was one order of magnitude greater than that for 1, and single-component magnetic relaxation behaviour was explained. In other words, it is possible to use f-f interactions to increase τ by one order of magnitude.

摘要

利用X射线晶体学以及静态和动态磁化率测量,对具有相同八配位环境和慢磁弛豫行为的双核Ln(III)-Pc三层夹心配合物(Dy(III)-Y(III):1和Dy(III)-Dy(III):2)的单分子磁体(SMM)行为进行了解释。特别是,从未在相同八配位环境的基础上讨论过双核Dy(III)-Pc三层夹心型SMM中4f电子之间的相互作用。我们的结果清楚地表明,1和2的Dy(III)离子位点是等效的,这与晶体结构一致。2在Dy(III)离子之间表现出铁磁相互作用。这清楚地证明了磁弛豫机制在很大程度上取决于双核体系中Dy(III)离子之间的偶极-偶极(f-f)相互作用。对于1和2,均观察到了磁化强度的量子隧穿(QTM)。然而,2的磁弛豫时间(τ)比1的大一个数量级,并且对单组分磁弛豫行为进行了解释。换句话说,利用f-f相互作用有可能将τ提高一个数量级。

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