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一种新型双核镧系元素配合物,由 8-羟基喹啉席夫碱和β-二酮构建而成:磁性和近红外发光性质。

A new family of dinuclear lanthanide complexes constructed from an 8-hydroxyquinoline Schiff base and β-diketone: magnetic properties and near-infrared luminescence.

机构信息

Department of Chemistry, Tianjin University, Tianjin, 300354, China.

出版信息

Dalton Trans. 2019 Jan 22;48(4):1392-1403. doi: 10.1039/c8dt04384a.

DOI:10.1039/c8dt04384a
PMID:30623947
Abstract

Six phenoxo-O bridged dinuclear lanthanide(iii) complexes have been assembled utilizing the 2-[(4-nitrophenyl)imino]methyl-8-hydroxyquinoline (HL) and dibenzoylmethane (Hdbm) ligands: [Ln2(dbm)4L2] (Ln = Nd (1), Eu (2), Gd (3), Tb (4), Dy (5) and Er (6)). Complexes 1 and 6 exhibit the characteristic emission peaks of the corresponding Nd3+ and Er3+ ions, respectively. Meanwhile, the excitation wavelength (470 nm) for complex 1 is located in the visible-light region, confirming a practical application value. The studies on magnetic properties reveal that complex 3 features a magnetocaloric effect with a magnetic entropy change of -ΔSm = 14.36 J kg-1 K-1 at 4 K for ΔH = 7 T. What's more, the dynamic magnetic studies for complex 5 show that it exhibits slow magnetic relaxation behavior, typical of SMM behavior, resulting in an energy barrier of ΔE/kB = 75 K with the pre-exponential factor τ0 = 2.2 × 10-7 s. Meanwhile, this research demonstrates that the magnetic properties can be modulated by regulating the electron-donating/withdrawing effects of the substituents on the ligands.

摘要

六种苯氧-O 桥联双核镧系(III)配合物已通过 2-[(4-硝基苯基)亚氨基]甲基-8-羟基喹啉(HL)和二苯甲酰甲烷(Hdbm)配体组装而成:[Ln2(dbm)4L2](Ln = Nd(1),Eu(2),Gd(3),Tb(4),Dy(5)和 Er(6))。配合物 1 和 6 分别表现出相应的 Nd3+和 Er3+离子的特征发射峰。同时,配合物 1 的激发波长(470nm)位于可见光区域,证实了其具有实际应用价值。磁性研究表明,配合物 3 在 4K 下,在 7T 的磁场变化下,磁熵变化为-ΔSm = 14.36 J kg-1 K-1,具有磁热效应。此外,配合物 5 的动态磁性研究表明,其表现出缓慢的磁弛豫行为,典型的单分子磁体(SMM)行为,导致能垒ΔE/kB = 75K,前指数因子 τ0 = 2.2×10-7s。同时,该研究表明通过调节配体上取代基的供电子/吸电子效应可以调节其磁性。

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