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二维羧酸盐桥联镧系配位聚合物:在检测铁、铬酸盐和硝基苯中展现出慢磁弛豫和发光特性。

2D carboxylate-bridged Ln coordination polymers: displaying slow magnetic relaxation and luminescence properties in the detection of Fe, CrO and nitrobenzene.

作者信息

Gao Wei, Liu Feng, Zhang Bao-Ying, Zhang Xiu-Mei, Liu Jie-Ping, Gao En-Qing, Gao Qing-Yu

机构信息

College of Chemical Engineering China University of Mining and Technology, Xuzhou, Jiangsu 221116, China.

出版信息

Dalton Trans. 2017 Oct 17;46(40):13878-13887. doi: 10.1039/c7dt03088f.

Abstract

Eight new 2D isostructural lanthanide coordination polymers (Ln-CPs), [Ln(HL)(HO)(NO)]·NO (1-Ln), Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Yb ions, HL = 4-(3,5-dicarboxylphenyl)-2-methylpyridine, were synthesized by using solvothermal methods and studied by structural analyses, magnetic analyses and luminescent probes. Crystallographic studies revealed that these compounds are 2D frameworks in which dinuclear units with double μ-syn,syn-carboxylate bridges are interlinked by single μ-trans,trans-carboxylate bridges from organic spacers. The layers are further stabilized and combined into 3D architectures through intra- and interlayer ππ stacking interactions and hydrogen bonding, respectively. Magnetic investigations indicated that the carboxylate bridges transmit intralayer antiferromagnetic coupling in 1-Nd, 1-Gd and 1-Ho but transmit intralayer ferromagnetic coupling in 1-Dy. Furthermore, 1-Dy also displays slow magnetic relaxation behavior with a high relaxation energy barrier (ΔU) of 100.7 K and a pre-exponential factor (τ) of 1.4 × 10 s under zero dc field. The luminescence investigations showed that CPs 1-Eu and 1-Tb can serve as highly selective and recyclable sensing materials for Fe, CrO and nitrobenzene. Thus, both 1-Eu and 1-Tb should be excellent candidates for multifunctional sensors.

摘要

通过溶剂热法合成了8种新型二维同构镧系配位聚合物(Ln-CPs),即[Ln(HL)(HO)(NO)]·NO(1-Ln),其中Ln = Nd、Sm、Eu、Gd、Tb、Dy、Ho和Yb离子,HL = 4-(3,5-二羧基苯基)-2-甲基吡啶,并通过结构分析、磁性分析和发光探针进行了研究。晶体学研究表明,这些化合物为二维框架结构,其中具有双μ-syn,syn-羧酸酯桥的双核单元通过来自有机间隔基的单μ-trans,trans-羧酸酯桥相互连接。这些层通过层内和层间的ππ堆积相互作用以及氢键分别进一步稳定并组合成三维结构。磁性研究表明,羧酸酯桥在1-Nd、1-Gd和1-Ho中传递层内反铁磁耦合,但在1-Dy中传递层内铁磁耦合。此外,1-Dy在零直流场下还表现出缓慢的磁弛豫行为,具有100.7 K的高弛豫能垒(ΔU)和1.4×10 s的预指数因子(τ)。发光研究表明,CPs 1-Eu和1-Tb可作为Fe、CrO和硝基苯的高选择性和可回收传感材料。因此,1-Eu和1-Tb均应是多功能传感器的优秀候选材料。

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