铽（III）-噻吩甲酰三氟丙酮-电化学聚合漆酚配合物的研究

研究了铽（III）和噻吩甲酰三氟丙酮（HTTA）形成的配合物与电化学聚合方 法得到的聚合漆酚（EPU）发生配位反应及pH = 10.2时形成配合物Tb(III)-TTA- EPU的组分和结构。红外光谱、X光电子能谱的测试表明Tb~(3+)分别与EPU，TTA~- 发生配位。元素分析和电感偶合等离子体发射光谱（AES）测定结果证明了每个 Tb~(3+)分别与EPU分子中1个链节单元的羟基和3个TTA~-发生配位，从而得到配合 物的结构。动态机械热分析（DMTA）表明发生配位反应后该配合物进一步交联，从 而难溶于大部分有机溶剂，其玻璃化转变温度和耐热性能均得到很大提高。我们对 其荧光性质进行了研究，发现常温下配合物在紫外光下发生强的荧光，主要是Tb~ (3+)离子的~5D_4→~7F_5的跃迁。讨论了溶剂、pH值对配合物荧光强度的影响。当 pH = 10.2时，合成的配合物有最好的荧光性质。

Studies on the Tb (III)-Thienyltrifluroacetone-Electropolyurushiol

Coordination polymer (Tb(III)-TTA-EPU) was formed at pH = 10.2 by reaction of EPU (M_w = 3160) with metalorganic complex NaTb (TTA)_4 prepared from terbium chloride isopropyl alcohol solution and thienyltrifluroacetone. The coordination polymer was characterized by FT-IR, XPS. Elemental analysis and AES indicate that each Tb~(3+) ion is coordinated by three TTA~- ions and two hydroxyls from one unit in the EPU molecule, making the coordination polymer cross-linked further. The results of DMTA show that the title polymer is insoluble in most of organic solvents and has a high glass transition temperature and high thermal resistance. The coordination polymer shows intense fluorescence at 545 nm under UV excitation at room temperature, which is attributed to the ~5D_4 → ~7F_5 transition of Tb~(3+) ions. The effects. of solvents and pH on the fluorescence intensity were investigated. The fluorescence spectrum indicates that the coordination polymer has good fluorescence properties at pH = 10.2.