稀土配合物RE(TPTZ)Cl3的合成、表征及荧光性能研究

首次以2,4,6-三吡啶基三嗪（TPTZ）与Sm, Eu, Tb和Dy氯化物反应，合成四种单一稀土配合物以及Tb分别1∶1掺Gd, Y, La的三种异核配合物。经元素分析、稀土络合滴定、摩尔电导率、红外光谱、紫外光谱和差热-热重测定表明，配合物的组成分别为RE（TPTZ）Cl3·3H2O（RE=Sm, Eu, Tb, Dy）和Tb0.5Ln0.5（TPTZ）Cl3·3H2O（Ln=Gd, Y, La）;TPTZ作为三齿配体与稀土离子配位，即中心环提供一个N原子，两个吡啶环分别提供一个N原子;配合物中3个水分子与稀土离子配位，1个Cl-在外界，2个在内界，为1∶1型电解质;配合物内外界可能为[RE（TPTZ）（H2O）3Cl2] Cl，稀土离子的配位数为8。配合物的荧光光谱测试表明，四种单一稀土配合物中，Tb配合物发光最强;三种1∶1掺杂异核Tb配合物荧光强度大于纯Tb配合物，表明Y3＋, La3＋和Gd3＋都可以敏化Tb3＋的发光，其中Gd3＋的敏化作用最强，Y3＋次之，La3＋最差。

Synthesis,Characterization and Fluorescence Properties of Rare Earth Complexes RE(TPTZ)Cl_3

The reaction of 2,4,6-tri(2-pyridyl)-1,3,5-triazine (TPTZ) with RECl3 in ethanol solution was studied. Seven solid coordination compounds of rare earth were synthesized. Their elemental analysis, rare earth complexometric titration, molar conduction, TG-DTA curve, IR spectra and UV spectra were studied. The results suggest that the composition of the complexes was RE(TPTZ)Cl3·3H2O(RE=Sm, Eu, Tb, Dy) and Tb0.5Ln0.5(TPTZ)Cl3·3H2O(Ln=Gd, Y, La), where TPTZ acts as a tridentate ligand with rare earth ion, the rare earth ion is eight-coordinate being bonded to the tridentate TPTZ, two Cl- anions and three water molecules, and the complexes-bounded may be ［RE(TPTZ)(H2O)3Cl2］·Cl and ［(Tb0.5Ln0.5)(TPTZ)(H2O)3Cl2］·Cl. They are all 1∶1 electrolytes in the DMF. The fluorescence spectra of the complexes were determined at room temperature. The results show that the fluorescence intensity of Tb3+ complex is the strongest among the four (Eu3+, Sm3+, Tb3+ and Dy3+) complexes. The lowest excitation state energy level of Tb3+ ion and the triplet state energy level of the ligand (TPTZ) match well. The absorbing energy of the ligand is effectively transferred to Tb3+ ion. The fluorescence intensity of terbium doped complexes (Tb3+ mixed by Gd3+, Y3+ and La3+) is stronger than that of terbium complex, showing that the fluorescence intensity of Tb3+ ion is raised by Gd3+, Y3+ and La3+ ions.