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由双功能连接体构建的一系列高稳定性镧系有机框架:合成、晶体结构以及磁性和发光性质

Series of Highly Stable Lanthanide-Organic Frameworks Constructed by a Bifunctional Linker: Synthesis, Crystal Structures, and Magnetic and Luminescence Properties.

作者信息

Peng Dong, Yin Lei, Hu Peng, Li Bao, Ouyang Zhong-Wen, Zhuang Gui-Lin, Wang Zhenxing

机构信息

Wuhan National High Magnetic Field Center & School of Physics , Huazhong University of Science and Technology , Wuhan , Hubei 430074 , People's Republic of China.

Key laboratory of Material Chemistry for Energy Conversion and Storage, School of Chemistry and Chemical Engineering , Huazhong University of Science and Technology , Wuhan , Hubei 430074 , People's Republic of China.

出版信息

Inorg Chem. 2018 Mar 5;57(5):2577-2583. doi: 10.1021/acs.inorgchem.7b02969. Epub 2018 Feb 21.

DOI:10.1021/acs.inorgchem.7b02969
PMID:29465993
Abstract

By utilizing a preselected functional ligand produced by 1 H-imidazole-4,5-dicarboxylic acid, three isostructural lanthanide coordination polymers (CPs), denoted as {[Ln(OH)(L)]·(DMF)·(HO)} (Ln = Gd (1), Eu (2), Dy (3); L = 1-(4-carboxybenzyl)imidazole-4-carboxylic acid), containing a 1D infinite [Ln(OH)] subchain have been successfully constructed. The highly connected mode between the multifunctional ligand and 1D building units is responsible for the exceptional chemical stability of three lanthanide CPs. In addition, a study of the magnetic properties reveals that 1 displays a large magnetic entropy change (-Δ S = 30.33 J kg K with T = 2 K and Δ H = 7 T). Furthermore, genetic algorithm and quantum Monte Carlo methods were combined to simulate the magnetic coupling parameters of compound 1, shedding light on the effect of linking bridges on magnetic propagation. 2 shows intense luminescence in the range of 350-710 nm. Comparably, magnetic studies of 3 reveal the existence of a metamagnetic transformation from an antiferromagnetic interaction to a ferromagnetic interaction along with a decrease in temperature. Through fitting of the results of HF-EPR measurements, a component of the g tensor is obtained, g = 16.4(5), indicating the large anisotropy of 3.

摘要

通过利用由1H-咪唑-4,5-二羧酸产生的预选功能配体,成功构建了三种同构的镧系配位聚合物(CPs),表示为{[Ln(OH)(L)]·(DMF)·(HO)} (Ln = Gd (1)、Eu (2)、Dy (3);L = 1-(4-羧基苄基)咪唑-4-羧酸),其包含一维无限[Ln(OH)]子链。多功能配体与一维构建单元之间的高度连接模式是三种镧系CPs具有出色化学稳定性的原因。此外,磁性研究表明1显示出大的磁熵变(T = 2 K且ΔH = 7 T时,-ΔS = 30.33 J kg K)。此外,结合遗传算法和量子蒙特卡罗方法模拟了化合物1的磁耦合参数,揭示了连接桥对磁传播的影响。2在350 - 710 nm范围内显示出强烈的发光。相比之下,对3的磁性研究表明,随着温度降低,存在从反铁磁相互作用到铁磁相互作用的变磁转变。通过对HF-EPR测量结果的拟合,获得了g张量的一个分量,g = 16.4(5)。这表明3具有大的各向异性。

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