溶剂调控的一维镧系配位聚合物与三羧酸配体的组装。

Solvent-regulated assemblies of 1D lanthanide coordination polymers with the tricarboxylate ligand.

机构信息

Laboratory of Coordination Chemistry, Shenyang University of Chemical Technology, Shenyang, 110142, People's Republic of China.

出版信息

Dalton Trans. 2014 Mar 7;43(9):3462-70. doi: 10.1039/c3dt52839a.

DOI:10.1039/c3dt52839a

PMID:24384992

Abstract

Solvothermal reactions of the tricarboxylic acid ligand, biphenyl-3,3',5-tricarboxylic acid (H3bpta), and rare earth nitrate (Ln(NO3)3·6H2O) in the presence of KOH or DMF produced eight 1D linear coordination polymers, namely, [La(bpta)(H2O)5·(H2O)3]n (), [Pr(bpta)(H2O)5·(H2O)2.5]n (), [Nd(bpta)(H2O)5·(H2O)1.75]n (), [Sm(bpta)(H2O)5·(H2O)0.5]n () and [Ln(bpta)(DMF)(H2O)3·(H2O)]n [Ln = Eu (), Gd (), Tb (), Dy ()]. The 1D chain further assembles into a 3D supramolecular network structure through hydrogen bonds and π-π stacking among chains. Complexes and display the typical emission spectra for lanthanide-centred luminescence. The optical properties of were analysed in detail and coincide well with the structural properties. The influence of temperature on the luminescence lifetime of has been studied and different non-radiative decay paths have been discussed. The magnetic properties show that and exhibit strong spin-orbit coupling, while weak antiferromagnetic coupling exists in .

摘要

在 KOH 或 DMF 的存在下，三羧酸配体联苯-3,3',5-三羧酸（H3bpta）和稀土硝酸盐（Ln(NO3)3·6H2O）的溶剂热反应产生了八个一维线性配位聚合物，分别为[La(bpta)(H2O)5·(H2O)3]n ()、[Pr(bpta)(H2O)5·(H2O)2.5]n ()、[Nd(bpta)(H2O)5·(H2O)1.75]n ()、[Sm(bpta)(H2O)5·(H2O)0.5]n ()和[Ln(bpta)(DMF)(H2O)3·(H2O)]n [Ln = Eu (), Gd (), Tb (), Dy ()]。一维链通过氢键和链间π-π堆积进一步组装成三维超分子网络结构。配合物和显示出典型的镧系中心发光的发射光谱。详细分析了的光学性质，与结构性质吻合良好。研究了温度对的荧光寿命的影响，并讨论了不同的非辐射衰减途径。磁性研究表明和表现出强烈的自旋轨道耦合，而在中存在弱的反铁磁耦合。