稀土与3-羧基苯磺酸、2-(4-吡啶基)-咪唑[4,5-f]菲咯啉构筑的双核配合物的合成、晶体结构及表征

Syntheses, Crystal Structures and Characterization of Binuclear Lanthanide Complexes with 3-Sulfobenzoate and 2-(4-Pyridyl)imidazole[4,5-f ]phenanthroline

以3-羧基苯磺酸根（3-SBA）和2-（4-吡啶基）-咪唑[4,5-f]菲咯啉（4-PDIP）为配体,用水热法合成了3种稀土配合物：[Ln2（3-SBA）2（4-PDIP）2（OH）2（H2O）4]·2H2O（Ln=Sm（1）,Eu（2）和Gd（3））。用X-射线单晶衍射分析方法测定了其晶体结构。配合物1~3为同构的双核分子。2个羟基以桥联方式连接2个Ln（Ⅲ）离子,3-SBA和4-PDIP以螯合双齿形式与Ln（Ⅲ）离子配位。双核分子之间通过氢键构筑成三维超分子结构。配合物1和3分别在545 nm和529 nm处出现来自于配体的荧光发射,对应于配体的π＊-π的跃迁。配合物2呈现Eu（Ⅲ）离子的特征发射,位于579、592、612、650和696 nm处的发射峰分别对应于5D0→7Fj（j=0~4）跃迁。

Taking 3-sulfobenzoate（3-SBA） and 2-（4-pyridyl）imidazole[4,5-f ]phenanthroline（4-PDIP） as the ligands,three lanthanide complexes, [Ln2（3-SBA）2（4-PDIP）2（OH）2（H2O）4]·2H2O（Ln=Sm（1）, Eu（2）, Gd（3）） were obtained by hydrothermal method. The crystal structures were determined by single crystal X-ray diffraction. The three complexes are binuclear molecules. In the complexes, two Ln （Ⅲ） ions are linked by two hydroxyl groups in bridging-bidentate coordination mode. 3-SBA and 4-PDIP ligands are coordinated with Ln（Ⅲ） ions by the chelating bidentate coordination mode. The three-dimensional supramolecular structure is formed through the hydrogen bonds between binuclear molecules. Complexes 1 and 3 display intense broad emission bands at 545 nm and 529 nm, respectively, which correspond to the π＊-π transition of the ligands. Complex 2 presents the characteristics emission of Eu （Ⅲ） ion. The narrow emission bands at 579, 592, 612, 650 and 696 nm are attributed to5D0→7Fj（j=0-4） transitions of the Eu（Ⅲ） ion, respectively. CCDC： 1046171, 1; 1046169, 2; 1046170, 3.