Family of Defect-Dicubane Ni(4)Ln(2) (Ln = Gd, Tb, Dy, Ho) and Ni4Y2 Complexes: Rare Tb(III) and Ho(III) Examples Showing SMM Behavior
Family of Defect-Dicubane Ni(4)Ln(2) (Ln = Gd, Tb, Dy, Ho) and Ni4Y2 Complexes: Rare Tb(III) and Ho(III) Examples Showing SMM Behavior
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缺陷二立方烷 Ni(4)Ln(2)（Ln = Gd、Tb、Dy、Ho）和 Ni4Y2 配合物系列：显示 SMM 行为的稀有 Tb(III) 和 Ho(III) 示例
DOI：
10.1021/ic402973g
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发表时间：
2014
影响因子：
4.6
通讯作者：
Tang Jinkui
中科院分区：
文献类型：
--
作者：
Zhao Lang;Wu Jianfeng;Ke Hongshan;Tang Jinkui
高氯酸镧（Ln = Gd, Tb， Dy和Ho）， NiCl2·6H2O和多齿希夫碱的反应导致了新型同构六核ni4ln2配合物的组装[Ln = Gd (1), Tb (2), Dy (3), Ho(4)]，具有前所未有的由两个缺陷-二亚苯单元组成的3d-4f金属拓扑结构。还分离了相应的含抗磁性iii原子的Ni4Y2(5)配合物，以辅助磁性研究。有趣的是，配合物2和3表现出SMM特性，4表现出缓慢的磁化弛豫。Ni-Y样品中没有频率相关的同相和非同相信号，这表明Ln离子对慢弛豫的贡献一定是有效的，正如之前在其他Ni-Dy样品中观察到的那样。然而，对于Ni-Tb和Ni-Ho导数，在零直流场下观察到χ″信号是值得注意的。事实上，这是第一次在Ni-Tb和Ni-Ho配合物中观察到这种行为。
Reactions of LnIIIperchlorate (Ln = Gd, Tb, Dy, and Ho), NiCl2·6H2O, and a polydentate Schiff base resulted in the assembly of novel isostructural hexanuclear Ni4Ln2complexes [Ln = Gd (1), Tb (2), Dy (3), Ho (4)] with an unprecedented 3d–4f metal topology consisting of two defect-dicubane units. The corresponding Ni4Y2(5) complex containing diamagnetic YIIIatoms was also isolated to assist the magnetic studies. Interestingly, complexes2and3exhibit SMM characteristics and4shows slow relaxation of the magnetization. The absence of frequency-dependent in-phase and out-of-phase signals for the Ni–Y species suggests that the Ln ions’ contribution to the slow relaxation must be effectual as previously observed in other Ni–Dy samples. However, the observation ofχ″signals with zero dc field for the Ni–Tb and Ni–Ho derivatives is notable. Indeed, this is the first time that such a behavior is observed in the Ni–Tb and Ni–Ho complexes.