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磁场下Dy(iii)单分子磁体的热稳定性和光致发光

Thermostability and photoluminescence of Dy(iii) single-molecule magnets under a magnetic field.

作者信息

Bi Ye, Chen Cheng, Zhao Yi-Fang, Zhang Yi-Quan, Jiang Shang-Da, Wang Bing-Wu, Han Jun-Bo, Sun Jun-Liang, Bian Zu-Qiang, Wang Zhe-Ming, Gao Song

机构信息

Beijing National Laboratory for Molecular Sciences , State Key Laboratory of Rare Earth Materials Chemistry and Applications , College of Chemistry and Molecular Engineering , Peking University , Beijing 100871 , China . Email:

Wuhan National High Magnetic Center , Huazhong University of Science and Technology , Wuhan 430074 , China.

出版信息

Chem Sci. 2016 Aug 1;7(8):5020-5031. doi: 10.1039/c6sc01157h. Epub 2016 May 12.

Abstract

A series of compounds [ADyL]·[solvent] composed of a dysprosium(iii) ion coordinated by four chelated naphthyridine-like ligands (L = 4-hydroxy-8-methyl-1,5-naphthyridine-3-carbonitrile) and an alkali metal ion (A = Na, K, Rb, Cs) were synthesized and characterized. They behave as single-molecule magnets under a zero dc field with an effective energy barrier of around 95 cm. Meanwhile, the main part, [ADyL], of these SMMs is thermostable and sublimable. The geometric structures of three sublimed compounds are identical to the original ones without solvents, which is confirmed by X-ray diffraction using single crystal and powder samples. The static and dynamic magnetic properties remain unchanged before and after sublimation. Luminescence measurements at 5-77 K were performed to verify the energy gap between low-lying states and to understand the pathway of the thermal relaxation process of magnetization, as well as to inspect the tiny variation in magnetic sublevels for the ground term of Dy(iii). The photoluminescence spectra under a magnetic field (0-36 T) for the Dy-SMMs are investigated for the first time. The energy splitting of the two lowest sublevels of the ground term H of Dy(iii) are analyzed using the Zeeman formula.

摘要

合成并表征了一系列由一个镝(iii)离子与四个螯合的萘啶类配体(L = 4-羟基-8-甲基-1,5-萘啶-3-腈)以及一个碱金属离子(A = Na、K、Rb、Cs)配位组成的化合物[ADyL]·[溶剂]。它们在零直流场下表现为单分子磁体,有效能垒约为95厘米。同时,这些单分子磁体的主要部分[ADyL]具有热稳定性且可升华。三种升华化合物的几何结构与无溶剂的原始结构相同,这通过使用单晶和粉末样品的X射线衍射得到证实。升华前后静态和动态磁性能保持不变。在5 - 77 K下进行发光测量,以验证低能态之间的能隙,了解磁化热弛豫过程的途径,并检查Dy(iii)基态磁亚能级的微小变化。首次研究了Dy - SMMs在磁场(0 - 36 T)下的光致发光光谱。使用塞曼公式分析了Dy(iii)基态H的两个最低亚能级的能量分裂。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/917b/6018642/1ec673a60ac4/c6sc01157h-f1.jpg

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