Synthesis And Properties Of Reactive Ternary Fluorescence Complexes Of Terbium And Europium As Well As Their Polymer Fluorescence Complexes

Rare earth elements possess luminescent, electric and magnetic properties due to their particular electron structure, and these properties can also be changed, modified and strengthened through interacting them with the ligands. Synthetic polymer possesses such advantages as rich raw materials resources, convenient synthesis, easy processing, strong pound-resistance, light weight and low cost. If connecting both advantages to synthesize rare earth polymer complexes, it is possible to develop new rare earth function materials that will have great application value in such fields as luminescence, display, military camouflage, electron photo carve and solar energy transference. Meanwhile, the fabrication of rare earth polymer fluorescence complexes belongs to cross research area of rare earth luminescence, organic coordination radical photo-sensitization and functional polymer synthesis, So going in for this field research possess not only important theory significance but also wide application prospect.In order to design and synthesize rare earth polymer fluorescence complexes with excellent luminescent properties, a series of new reactive rare earth (terbium and europium) ternary organic fluorescence complexes were firstly synthesized, and then a series of new rare earth (terbium and europium) polymer fluorescence complexes were fabricated through copolymerizing these complexes to other synthetic monomers by means of the technological routes from coordination to polymerization. Their molecular compositions were confirmed by means of elemental analysis and EDTA titrimetric method;their molecular structures were characterized by FT-IR and UV spectroscopies;their thermal properties were studied by thermal analysis instrument, and also studied was the mechanism that the reactive terbium and europium ternary organic fluorescence complexes influenced on the thermal stability;their luminescent properties were investigated by means of fluorescence instrument, and also analyzed was the synergy of reactive ligands in the luminescence process;the relationships between luminescent intensity ofthe polymer complexes of terbium and europium and the content of reactive complexes monomers were studied by the regressive analysis method, and also discussed was the synergy mechanism of the polymer substrates in the luminescence process of polymer fluorescence complexes of terbium and europium.The main works are as follows:1. Fifty-two species reactive ternary organic fluorescence complexes of terbium and europium have firstly been synthesized, its fluorescence spectral characteristics had nothing to do with the ligands and emitted the characteristic red and green light of europium and terbium, respectively;The ability that the ligands transfer energy to the central terbium and europium ions has something to do with their coordination structure, and the same reactive ligand has different ability of producing synergy in the different complexes. We found the principle that the aromatic carboxylic acid transfered energy to the central terbium and europium ions, and culled the reactive ternary fluorescence complexes of terbium and europium with the best thermal stability and the highest luminescent intensity.2. Fifty-five species polymer fluorescence complexes of terbium and europium have firstly been fabricated by means of the technological routes from coordinating to polymerizing, the luminescent intensity of all synthesized polymer complexes of terbium and europium increase with the increment of the content of complexes monomers in the range of experiment, and the luminescent intensity of the complexes with polyethyl acrylate > that of the complexes with polybutyl methyl acrylate > that of the complexes with polystyrene. The fluorescent spectral characteristics of all synthesized polymer complexes of terbium and europium have nothing to do with the monomers, and appear the characteristic green and red fluorescence of terbium and europium, respectively.3. This dissertation firstly used the regressive analysis method to study the relationships between luminescent intensity of the polymer fluorescence complexes of terbium and europium and the content of reactive complexes monomers, and obtained the regressive equations, andused the R test method to prove their relativity, and also used these regressive equations to forecast the influence tendency of the content of reactive complexes monomers on the luminescent intensity of the polymer fluorescence complexes of terbium and europium.4. The synergy of reactive ligands in the luminescence process was discussed. The reactive ligands were joined into the fluorescence complexes of terbium and europium as the secondary ligands to form a new stable structure with the first ligands, and also harmonized the absorption energy of the first ligands to transfer to the rare earth ions. It can also occupy the position of water ligand to eliminate the non-radiation effects caused by water, and enable the luminescent intensity of the reactive ternary fluorescence complexes to be greater than that of secondary fluorescence complexes.5. The mechanism that the reactive ternary fluorescence complexes of terbium and europium influenced on the thermal stability of polymer substrates was discussed. The reactive ternary fluorescence complexes of terbium and europium were joined into the molecules of polyethyl acrylate, polybutyl methyl acrylate and polystyrene, and caused the polymer chain to crosslink to increase the rigidity of them. Moreover, their molecules that contained the first ligands of aromatic carboxylic acids, 1,10-Phenanthroline and thenoyltrifluoro-acetone with the double bond and aromatic ring structure can also increase the rigidity of polymer molecule structure, thereby it is helpful to enhance the thermal stability of polymer fluorescence complexes of terbium and europium.6. The synergy mechanism of polymer substrates for the luminescence ability of polymer fluorescence complexes of terbium and europium was investigated. The structure units (ethyl acrylate, butyl methyl acrylate and styrene) of polymer chain can sensitize the luminescence of terbium and europium ions. The synergy ability sequence of polymer substrates in the luminescent process of polymer complexes is as follows: polyethyl acrylate substrates > polybutyl methyl acrylate substrates > polystyrene substrates.