Xie Shang-Fang, Huang Li-Qian, Zhong Li, Lai Bi-Lin, Yang Meng, Chen Wen-Bin, Zhang Yi-Quan, Dong Wen
Guangzhou Key Laboratory for Environmentally Functional Materials and Technology, School of Chemistry and Chemical Engineering , Guangzhou University , Guangzhou 510006 , P. R. China.
Jiangsu Key Laboratory for NSLSCS, School of Physical Science and Technology , Nanjing Normal University , Nanjing 210023 , P. R. China.
Inorg Chem. 2019 May 6;58(9):5914-5921. doi: 10.1021/acs.inorgchem.9b00260. Epub 2019 Apr 22.
Four isostructural dinuclear lanthanide complexes based on 4-azotriazolyl-3-hydroxy-2-naphthoic acid (HATNA) and 3-hydroxy-2-naphthoic acid (HNA) ligands, {[Ln(HATNA)(HNA)(HO)]·6DMF} (Ln = Dy (1), Tb (2), Sm (3), Eu (4); DMF = N, N-dimethylformamide) have been prepared and characterized by X-ray diffraction crystallography, dc/ac magnetic characterization, and fluorescent spectrometry. The crystallographic data reveal dinuclear lanthanide cores of complexes 1-4, bridged by phenoxo and μ carboxyl groups. Each nine-coordinated Ln(III) ion is located in a slightly distorted monocapped square antiprism. The ligand of HATNA displays a unique antenna effect in complex 4. Complexes 1-3 display only two ligand-centered fluorescent emissive peaks around 450 and 600 nm, and complex 4 shows four characteristic Eu(III)-centered emission bands at 593, 618, 653, and 698 nm under excitation at 348 nm. Complex 1 exhibits single-molecule magnet behavior that is rationalized through ab initio calculations.
基于4-偶氮三唑基-3-羟基-2-萘甲酸（HATNA）和3-羟基-2-萘甲酸（HNA）配体合成了四种同构双核镧系配合物{[Ln(HATNA)(HNA)(HO)]·6DMF}（Ln = Dy (1)、Tb (2)、Sm (3)、Eu (4)；DMF = N,N-二甲基甲酰胺），并通过X射线衍射晶体学、直流/交流磁性表征和荧光光谱对其进行了表征。晶体学数据揭示了配合物1-4的双核镧系核心，由苯氧基团和μ羧基桥连。每个九配位的Ln(III)离子位于一个轻微扭曲的单帽四方反棱柱中。HATNA配体在配合物4中表现出独特的天线效应。配合物1-3在450和600 nm左右仅显示两个以配体为中心的荧光发射峰，配合物4在348 nm激发下在593、618、653和698 nm处显示四个以Eu(III)为中心的特征发射带。配合物1表现出单分子磁体行为，通过从头算计算对其进行了合理解释。
