以硝酸锌与3,4’-联苯二甲酸(3,4’-H2dpdc), 4,4’-联吡啶(4,4’-bpy)为反应物, 以水为溶剂, 适当调节pH值, 通过水热反应, 得到配合物［Zn(3,4’-Hdpdc)2(4,4’-bpy)］(Zn-MOF)。 利用X射线单晶衍射测试分析确定了该配合物是由4,4’-bpy配体桥联Zn(Ⅱ)离子形成的 “Z”形链结构, 属于单斜晶系, C2/c空间群。 在278 nm激发下, Zn-MOF的荧光发射光谱在341～537 nm范围出现宽发射峰, 最强发射峰波长406 nm, 属于配体的π*—π跃迁。 研究了该配合物对Tb(Ⅲ)离子发光性能的影响。 实验结果表明, Zn-MOF可敏化甲醇和水溶液中的Tb(Ⅲ)离子, 使Tb(Ⅲ)离子的特征荧光发射峰增强。 在荧光光谱490, 545, 585和624 nm出现强的线状发射峰, 对应于Tb(Ⅲ)离子的5D4→7FJ (J=6～3)跃迁。 最强发射峰位于545 nm (5D4→7F5), 为绿光。 Zn-MOF可用作荧光探针检测甲醇和水溶液中的Tb(Ⅲ)离子。

A metal-organic framework ［Zn (3,4’-Hdpdc)2(4,4’-bpy)］ (Zn-MOF) has been synthesized by hydrothermal reaction with the Zn(NO3)2·6H2O, 3,4’-biphenyl dicarboxylic acid (3,4’-H2dpdc) and 4,4’-bipyridine (4,4’-bpy) , and its crystal structure was confirmed by X-ray single crystal diffraction. The complex was the monoclinic system, C2/c space group. The complex had a “Z”-shaped chain structure formed by the 4,4’-bpy ligand and Zn(Ⅱ) ion. The Zn-MOF exhibited intense ligand-based blue luminescence with the maximum excitation wavelength of 278 nm, and the emission band was in the range of 341~537 nm from the π*—π transition of the ligand. The emission maximum was at 406 nm. The luminescence properties of the complex toward Ln(Ⅲ) metal ions in methanol/aqueous solutions were studied. Fluorescence spectrum show the characteristic emission peaked of Tb (Ⅲ) ions at 490, 545, 585 and 624 nm, which corresponded to 5D4→7FJ (J=6～3) transitions of Tb (Ⅲ), the strongest emission peaked at 545 nm (5D4→7F5), for the green light. The experimental results showed that the Zn-MOF can sensitize the Tb(Ⅲ) ion in the methanol solution and in water, and thus the compound can be used as a fluorescent probe to detect Tb(Ⅲ) ions in methanol solutions and in water.