Katoh Keiichi, Asano Rina, Miura Akira, Horii Yoji, Morita Takaumi, Breedlove Brian K, Yamashita Masahiro
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-ku, Sendai, Miyagi 980-8578, Japan.
Dalton Trans. 2014 Jun 7;43(21):7716-25. doi: 10.1039/c4dt00042k. Epub 2014 Mar 7.
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.
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。