Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]•0.5bipy•3H2O配合物的合成、晶体结构及荧光性质

在水-乙醇混合体系中, 以2-羰基丙酸水杨酰腙(C₁₀H₁₀N₂O₄)、2,2-联吡啶(C₁₀H₈N₂, 简写bipy)与Eu(NO₃)₃?4H₂O反应, 首次培养出黄色单晶Eu(C₁₀H₉N₂O₄)(C₁₀H₈N₂O₄)(H₂O)₃]?0.5bipy?3H₂O. 该晶体属三斜晶系, 空间群为P-1, 晶胞参数a＝0.93392(16) nm, b＝1.3100(2) nm, c＝1.3895(2) nm, α＝97.205(3)°, β＝105.411(2)°, γ＝106.364(2)°, V＝15.35(2) nm³, Z＝2, μ＝2.118 mm^－1, D_c＝1.686 Mg/m³, F(000)＝786, R＝0.0116, wR＝0.0507, GOF＝0.995. 晶体测试结果表明, 该单晶结构为铕的9配位配合物, 两个2-羰基丙酸水杨酰腙分别以负一价和负二价酮式和三个水分子同时参与配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和C＝N中的氮与Eu^3＋配位, 形成两个共边的稳定五元环, 另三个配位原子则分别来自三个水分子中的氧原子, 该配合物在空间呈扭曲的单帽四方反棱柱, 而在不对称单位中还有游离的一个2,2-联吡啶分子和三个水分子, 这些游离分子与配位分子之间存在大量分子内和分子间氢键, 整个分子在空间呈三维网状结构. 发光性能测试表明该配合物具有很好的荧光性质.

Synthesis, Crystal Structure and Fluorescence Property of [Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]•0.5bipy•3H2O

Eu(NO₃)₃?4H₂O has reacted with 2-oxopropionic acid salicyloyl hydrazone (C₁₀H₁₀N₂O₄) and 2,2'-bipyridyl (C₁₀H₈N₂, bipy) to obtain a yellow prismatic crystal of the complex Eu(C₁₀H₉N₂O₄)- (C₁₀H₈N₂O₄)(H₂O)₃]?0.5bipy?3H₂O for the first time in H₂O-C₂H₅OH mixed solvent. The compound crystallized in the triclinic system with space group P-1 and parameters a＝0.93392(16) nm, b＝1.3100(2) nm, c＝1.3895(2) nm, α＝97.205(3)°, β＝105.411(2)°, γ＝106.364(2)°, V＝15.35(2) nm³, Z＝2, μ＝2.118 mm^－1, D_c＝1.686 Mg/m³, F(000)＝786, R＝0.0116, wR＝0.0507 and GOF＝0.995. In the structure, europium atom is 9-coordinated by carboxyl O and acyl O atoms and azomethine N atom of two tridentate C₁₀H₁₀N₂O₄ ligands negative univalent and bivalent and three water molecules to form two stable five-membered rings sharing one side in ketone form. The coordination polyhedron around Eu^3＋ was described as a single cap square antiprism. In the crystal cell, there are one free bipy and three water molecules connected with 2-oxopropionic acid salicyloyl hydrazone and coordinated water molecule by hydrogen bonds. The complex formed a three-dimensional super molecule in space through hydrogen bonds. The test of luminescence performance of the complex has shown it has good fluorescence property.