一系列（3,6）连接的镧系有机骨架的结构、发光和磁性性质。

Structures, luminescent and magnetic properties of a series of (3,6)-connected lanthanide-organic frameworks.

机构信息

Department of Chemistry, Key Laboratory of Advanced Energy Material Chemistry, MOE, TKL of Metal and Molecule Based Material Chemistry, and Synergetic Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China.

出版信息

Dalton Trans. 2014 Jan 28;43(4):1814-20. doi: 10.1039/c3dt52305e.

DOI:10.1039/c3dt52305e

PMID:24253449

Abstract

Through hydrothermal reactions with corresponding lanthanide nitrates and 4-(4-carboxyphenylsulfonyloxy)-3-metnoxybenzoic acid (H2vspc), seven novel three-dimensional (3D) lanthanide-organic frameworks ([Ln(vspc)(Hvspc)(H2O)]n [Ln = Pr (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6) and Er (7)]) have been synthesized and structurally characterized. All of them are isostructural and crystallize in the monoclinic crystal system, P21/c space group. Their structures feature a (3,6)-connected topological network, in which Ln(3+) were connected by carboxylate groups to give a 1D lanthanide chain, and the adjacent chains are further spanned by vspc(2-) and Hvspc(-) anions to form a 3D framework. The luminescent properties and lifetimes of 2 (Eu(III)), 4 (Tb(III)), and 5 (Dy(III)) have been studied, and the corresponding luminescent lifetimes are 0.53, 0.99 and 0.014 ms, respectively. The magnetic investigations reveal that compound displays weak antiferromagnet interaction, 4 and 5 exhibit ferromagnetic coupling, and compound 5 exhibits slow magnetic relaxation behavior.

摘要

通过与相应的镧系硝酸盐和 4-(4-羧基苯磺酰氧基)-3-甲氧基苯甲酸（H2vspc）的水热反应，合成并结构表征了七个新型的三维（3D）镧系有机框架([Ln(vspc)(Hvspc)(H2O)]n[Ln=Pr(1)，Eu(2)，Gd(3)，Tb(4)，Dy(5)，Ho(6)和 Er(7)])。它们都是同构的，结晶于单斜晶系，P21/c 空间群。它们的结构特征为(3,6)-连接的拓扑网络，其中 Ln(3+)通过羧酸盐基团连接形成一维镧系链，相邻的链进一步由 vspc(2-)和 Hvspc(-)阴离子跨越形成 3D 骨架。研究了 2(Eu(III))、4(Tb(III))和 5(Dy(III))的发光性质和寿命，相应的发光寿命分别为 0.53、0.99 和 0.014 ms。磁性研究表明，化合物显示出弱的反铁磁相互作用，4 和 5 表现出铁磁耦合，化合物 5 表现出缓慢的磁弛豫行为。