Synthesis And Characterization Of Luminescent Terbium(Ⅲ) Complexes And Application Of Their Fluorescence System In Solution

This thesis is aimming at studying on fluorescence properties and applications of fluorescence systems of terbium (III) complexes in solution and consists of the following six parts:1. A brief review of the development on the theories and applications of the luminescent lanthanide complexes was given.2. A new Schiff base ligand, 3-tryptimino-1-phenyl-butan-1-one (TPB), was synthesized. Its fluorescence intensity with terbium(III) was greatly enhanced by addition of 1,10-phenanthroline (Phen) into the acetonitrile solution. Spectrofluorimetric determination of trace amounts of Tb³⁺ was performed based on the phenomenon. Under optimal conditions, the fluorescence intensities varied linearly with the concentration of Tb³⁺ in the range of 2.0×10^-6-7.0×10^-6mol·L^-1 with a detection limit of 2.4×10^-9mol·L^-1. Interference of some rare earth ions was described. This method was applied to the determination of trace amounts of terbium(III) in a high purity Y₂O₃ matrix. The mechanism of fluorescence enhancement was also studied.3. A new Schiff base ligand: 3- (naphthalene-2-ylimino) -1-phenylbutan-1-one (NPB) was synthesized. Its fluorescence intensity with terbium (HI) was greatly enhanced by the addition of 1,10-phenanthroline (Phen) or 2,2'-bipyridine (Bipy) in the chloroform solution. The mechanism of fluorescence enhancement was studied. The results indicate the formation of the ternary complex NPB-Phen-Tb or NPB-Bipy-Tb.4. A sensitive fluorescence enhancement system was developed for the determination of zinc (IT). The fluorescence intensity of the Tb-N-(2-Pyridinyl) ketoacetamide (PKA) system was greatly enhanced by the addition of triethylamine (Et₃N) and zinc nitrate in the methanol solution. Under optimal conditions, the fluorescence intensities varied linearly with the concentration of Zn²⁺ in the range of 8.0×10^-7-5.0×10^-6mol·L^-1 with a detection limit of 9.9×10^-8mol·L^-1. The interferences of some substances were described. This method was applied to the determination of amounts of Zn²⁺ in soybean, rice and wheat, respectively. The results showed that the proposed procedure is a high selective, simple, and rapid method to the determination of Zn²⁺ ion. The mechanism of fluorescence enhancement was also studied.5. 3,3,7,7-Tetra[N-ethyl-N-benzyl(acetamide)-2-oxymethyl]-5-oxanonane(EBAOO) and its terbium complex have been synthesized. The crystal structures of the complex were determined: [Tb(EBAOO)]₂[Tb(NO₃)₅]₃·H₂O. In the structure, the rare earth ion satisfies nine coordination. The luminescence of the complex is noticeable enhanced upon complexation with Ag⁺, which is due to the suppressing of photoinduced electron transfer (PET) process. Therefore, the terbium complex can be the generation of silver selective fluorescent probe.6. A simple, convenient method was described here for preparation of pentasubstituted pyrroles derivative using Mn(OAc)₃·2H₂O or Mn(OAc)₂·4H₂O at atmosphere.