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对称三桥联双核 3d-4f 单分子磁体的合理设计策略。

Strategy for the rational design of asymmetric triply bridged dinuclear 3d-4f single-molecule magnets.

机构信息

Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Granada, Av. Fuentenueva S/N, 18071 Granada, Spain.

出版信息

Inorg Chem. 2011 Aug 1;50(15):7268-73. doi: 10.1021/ic2008599. Epub 2011 Jun 29.

DOI:10.1021/ic2008599
PMID:21714490
Abstract

Three triply bridged M(II)-Dy(III) dinuclear complexes, [Ni(μ-L)(μ-OAc)Dy(NO(3))(2)] 1, [Zn(μ-L)(μ-OAc)Dy(NO(3))(2)] 2, and [Ni(μ-L)(μ-NO(3))Dy(NO(3))(2)]·2CH(3)OH 3 were prepared with a new and flexible compartmental ligand, N,N',N″-trimethyl-N,N″-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylene triamine (H(2)L), containing N(3)O(2)-inner and O(4)-outer coordination sites. These complexes have diphenoxo/acetate (1 and 2) or diphenoxo/nitrate (3) asymmetric bridging fragments. Compounds 1 and 3 exhibit ferromagnetic interaction between Ni(2+) and Dy(3+) ions and frequency dependence of the out-of-phase (χ″(M)) alternating current (ac) susceptibility signal characteristic of single-molecule-magnet behavior. The energy barriers Δ/k(B) for compound 3 under zero and 1000 Oe applied direct current (dc) magnetic fields were estimated from the Arrhenius plots to be 7.6 and 19.1 K, respectively.

摘要

三种三桥联的 M(II)-Dy(III)双核配合物，[Ni(μ-L)(μ-OAc)Dy(NO(3))(2)] 1，[Zn(μ-L)(μ-OAc)Dy(NO(3))(2)] 2，和[Ni(μ-L)(μ-NO(3))Dy(NO(3))(2)]·2CH(3)OH 3，是用一种新的、灵活的分隔配体，N,N',N″-三甲基-N,N″-双(2-羟基-3-甲氧基-5-甲基苄基)二乙三胺（H(2)L），与 N(3)O(2)-内和 O(4)-外配位位点合成的。这些配合物具有二苯氧基/乙酸盐（1 和 2）或二苯氧基/硝酸盐（3）不对称桥联片段。化合物 1 和 3 表现出 Ni(2+)和 Dy(3+)离子之间的铁磁相互作用，以及外相（χ″(M))交流（ac）磁化率信号的频率依赖性，这是单分子磁体行为的特征。在零和 1000 Oe 直流（dc）磁场下，化合物 3 的能量势垒 Δ/k(B)分别从 Arrhenius 图中估计为 7.6 和 19.1 K。

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