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Three Types of Lanthanide Coordination Polymers with Methylmalonate and Isonicotinate as Coligands: Structures, Luminescence, and Magnetic Properties
Crystal Growth & Design ( IF 3.8 ) Pub Date : 2017-10-26 00:00:00 , DOI: 10.1021/acs.cgd.7b01341
Zhong-Yi Li 1 , Yuan-Qing Cao 1 , Jing-Yu Li 2 , Xiang-Fei Zhang 1 , Bin Zhai 1 , Chi Zhang 1 , Fu-Li Zhang 1 , Guang-Xiu Cao 1
Affiliation  

Three types of lanthanide coordination polymers based on mixed methylmalonic acid (H2MMA) and isonicotinic acid (HINA), two-dimensional (2D) [Ln2(MMA)2(INA)2(H2O)3]n (Ln = Eu (1); Gd (2)) and [Ln(MMA)(INA)(H2O)2]n (Ln = Gd (3); Tb (4)) as well as one-dimensional (1D) [Dy(MMA)(INA)(H2O)2]n (5), have been hydrothermally synthesized, which can be controlled by the usage amount of H2MMA or the type of Ln3+ ion. Complexes 1 and 2 contain two kinds of 1D lanthanide chain units (wave and linear), which are alternately linked by the MMA2– and INA ligands to form a 2D layer structure. Complexes 3 and 4 also have a 2D layer structure, consisting of 1D linear lanthanide chain units, MMA2– and INA linkers. Compound 5 shows a 1D linear chain structure, in which the neighboring Dy3+ ions are fastened by the carboxylate groups from MMA2– and INA ligands. The magnetic studies reveal the presence of ferromagnetic Gd···Gd coupling in the 1D chain units of 2 and 3, which display significant cryogenic magnetocaloric effects with a maximum −ΔSm value of 34.32 J kg–1 K–1 at 3 K and 36.02 J kg–1 K–1 at 2 K for ΔH = 7 T, respectively. Furthermore, the solid-state photophysical properties of 1 and 4 exhibit strong characteristic Eu3+ and Tb3+ photoluminescent emission in the visible region, indicating that Eu- and Tb-based luminescences are sensitized effectively by the energy transfer from the INA ligand to the metal centers.

中文翻译:

丙二酸甲酯和异烟酸酯作为配体的三种镧系配位聚合物:结构,发光和磁性

基于混合的甲基丙二酸(H 2 MMA)和异烟酸(HINA)的三种镧系配位聚合物,二维(2D)[Ln 2(MMA)2(INA)2(H 2 O)3 ] n(Ln = Eu(1); Gd(2))和[Ln(MMA)(INA)(H 2 O)2 ] n(Ln = Gd(3); Tb(4))以及一维(1D) [Dy(MMA)(INA)(H 2 O)2 ] n5),已经水热合成,可以通过使用H 2 MMA的量或Ln 3+离子的类型来控制。配合物12包含2种1D镧系链单元(波和直链),其交替地由MMA联2-和INA -配体,以形成2D层结构。配合物34也有一个2D层结构,由一维的线性镧系链单元,MMA 2-和INA -接头。化合物5显示一维线性链结构,其中相邻的Dy 3+离子通过羧酸酯基团从MMA紧固2-和INA -配体。磁性研究揭示的存在铁磁的Gd ...中的一维链单元耦合的Gd 23,其显示具有最大-Δ显著低温磁效应小号的34.32值J千克-1 ķ -1在3 K对于ΔH = 7 T,在2 K时分别为36.02 J kg –1 K –1。此外,14的固态光物理性质表现出很强的特征Eu 3+和Tb 3+在可见光区域的光致发光发射,表明基于铽的Eu和luminescences被有效地从INA能量转移敏化-配体与金属中心。
更新日期:2017-10-26
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