Hydroxide-bridged five-coordinate Dy(III) single-molecule magnet exhibiting the record thermal relaxation barrier of magnetization among lanthanide-only dimers.
Hydroxide-bridged five-coordinate Dy(III) single-molecule magnet exhibiting the record thermal relaxation barrier of magnetization among lanthanide-only dimers.
复制标题
氢氧化物桥联五配位 Dy-III 单分子磁体在纯镧系元素二聚体中表现出创纪录的磁化热弛豫势垒
DOI：
10.1039/c6sc03621j
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发表时间：
2017-02-01
期刊：
影响因子：
8.4
通讯作者：
Gao S
中科院分区：
文献类型：
--
作者：
Xiong J;Ding HY;Meng YS;Gao C;Zhang XJ;Meng ZS;Zhang YQ;Shi W;Wang BW;Gao S
合成了具有短 Dy-O 键的氢氧化物桥联五配位镝(iii)二聚体。使用大的受阻酚配体合成了氢氧桥中心对称 DyIII 二聚体，每个 DyIII 都是五配位的。磁性研究表明，该化合物表现出单离子起源的缓慢磁弛豫以及磁耦合簇的阶梯状磁滞。在没有静磁场的情况下，磁化热弛豫势垒为 721 K，而报道的仅 4f 二聚体中分子内磁相互作用非常大。为了了解化合物的电子结构，进行了更大活性空间的 CASSCF 计算。热弛豫区和量子隧道区很好地分离，代表了研究具有分子内 Dy-Dy 磁相互作用的 SMM 弛豫机制的良好模型。
A hydroxide-bridged five-coordinate dysprosium(iii) dimer with short Dy–O bonds was synthesized. A hydroxide-bridged centrosymmetric DyIII dimer with each DyIII being five-coordinated has been synthesized using bulky hindered phenolate ligands. Magnetic studies revealed that this compound exhibits a slow magnetic relaxation of a single-ion origin together with a step-like magnetic hysteresis of the magnetic coupled cluster. The thermal relaxation barrier of magnetization is 721 K in the absence of a static magnetic field, while the intramolecular magnetic interaction is very large among reported 4f-only dimers. CASSCF calculations with a larger active space were performed to understand the electronic structure of the compound. The thermal relaxation regime and the quantum tunneling regime are well separated, representing a good model to study the relaxation mechanism of SMMs with intramolecular Dy–Dy magnetic interactions.