【作者】 王正祥；

【导师】 舒万艮； 陈洪；

【作者基本信息】 中南大学 ， 应用化学， 2004， 博士

【摘要】 稀土有机配合物发光是无机发光与有机发光、生物发光的交叉学科,有着重要的理论研究意义和实际应用价值。稀土离子具有丰富的能级和4f跃迁特性,使稀土离子成为一个巨大的发光宝库,为高新技术提供了许多性能优越的发光材料和激光材料。本文研究的铕、铽荧光配合物是指能够吸收辐射能产生光致发光的稀土有机配合物,涉及的第一配体主要为相对廉价的苯甲酸系列、发光强度较高的β-二酮类,并采用掺杂廉价的稀土离子的手段提高发光强度和降低成本,在此基础上,利用“原位法”合成技术,在双酚A环氧丙烯酸酯（EA）基质中,制备了相应的具有良好分散性的荧光剂,并成功的应用于光固化荧光防伪油墨中,制备了环保型的光固化荧光防伪油墨,最后对荧光猝灭效应及机理进行了研究。因此,本文的主要研究工作包括如下几个方面。 1.以均相沉淀法合成了铕红色荧光配合物和铽绿色荧光配合物,对其荧光性能进行了研究 （1）合成了铕-苯甲酸-邻菲咯啉、铕-噻吩甲酰三氟丙酮-邻菲咯啉三元配合物和铕-噻吩甲酰三氟丙酮-丙烯酸（或磺基水杨酸）-邻菲咯啉四元混配配合物,利用红外光谱、元素分析、荧光光谱及差热-热重谱对配合物进行了表征。荧光光谱表明:上述铕红色荧光配合物的荧光强度由强到弱的顺序如下:Eu（TTA）₃Phen（TTA:噻吩甲酰三氟丙酮,Phen:邻菲咯啉）,Eu（AA）（TTA）₂Phen（AA:丙烯酸）,Eu（BA）₃Phen（BA:苯甲酸）,Eu（AA）₂（TTA）Phen,Eu（TTA）SsalPhen（Ssal:磺基水杨酸）,其中Eu（AA）_x（TTA）_3-xPhen及Eu（TTA）（Ssal）Phen四元配合物体系的合成和荧光性能的研究,尚未见文献报道。 （2）合成了铽-均苯四甲酸（和偏三苯甲酸）、铽-对氨基苯甲酸和Tb-PMDMBA（PMDMBA=均苯四甲酸改性双酚A环氧丙酸酯）配合物,利用红外光谱、元素分析、荧光光谱及差热-热重谱对配合物进行了表征。上述铽绿色荧光配合物的荧光强度由强到弱的顺序如下:Tb（o-A）₃（o-A:邻氨基苯甲酸）,Tb（PMA）_3/4（PMA:均苯四甲酸）～Tb₂（Ssal）₃,Tb（p-A）（p-A:对氨基苯甲酸）,Tb（TMA）（TMA:偏三苯甲酸）,Tb-PMDMBA。其中Tb-PMDMBA的合成和荧光性能的研究尚未见文献报道,该配合物表现为强的铽离子的荧光发射。更多还原

【Abstract】 The study on the luminescence of rare earth complex, being the cross science of the luminescence of inorganic materials, organic materials and organism, is very important for the fundamental and applied research. The rare earth ion is a great treasure of luminescent materials since its abundant energy levels and 4f transition characteristics, and the rare earth elements provide a lot of luminescent materials and laser materials with good properties for high-new technique. The luminescence complexes of europium and terbium studied in this paper related to ones that can absorb radiant energy and can produce photoluminescence. The first ligands rated to these complexes principally are inexpensive benzoic acid and its derivatives, such as 8-diketones, which have good luminescent performance. Luminescent intensity of the complexes is improved and the cost is lowered by doping inexpensive no-fluorescent inert ions. Fluorescent agents with good disperse were prepared in the matrix of bisphenol A epoxy acrylate resin by in-situ and were successfully used in falsification-resistant inks, and fluorescent falsification-resistant inks with function of environment protection were prepared. At last, the fluorescent quenching mechanism was studied. Our main works are as followings:1. We synthesized the Europium complexes with red fluorescence and Terbium complexes with green fluorescence by using homogeneous precipitation and studied their fluorescent properties（1） Eu_1-xLn_x（BA）₃Phen, Eu_1-xLn_x（TTA）₃Phen （X=molar fraction of doping elements, Ln=Gd, La and Y, BA=benzoic acid, TTA=Thenoyltrifluoroacentone, Phen=1,10-phenanthroline） ternary complexes, Eu （AA）_x（TTA）_1-xPhen and Eu （TTA） SsalPhen （AA=crylic acid, Ssal=sulfosalicylic acid, X=1, 2） tetra-complexes were synthesized. Their properties were characterized by IR spectra, elemental analysis, fluorescent spectra and TG-DTA spectra. All of above complexes can emit characteristic fluorescence of europium ions. Fluorescence spectra showed that above Europium complexes have the order of fluorescent intensity from strongest to weakest: Eu（TTA）₃Phen, Eu（AA）（TTA）₂Phe, Eu（BA）₃Phen, Eu（AA）₂（TTA）Phen,Eu（TTA）SsalPhen. Synthesis and fluorescent properties of Eu（AA）x（TTA）3.xPhen and Eu（TTA）SsalPhen complexes were not reported in the literatures.（2） Complexes of Terbium with pyromellitic acid （PMA）（and trimellitic acid, TMA）, complexes of Terbium with p-aminobenzoic acid （p-A） et al were synthesized. Their properties were characterized by IR spectra, elemental analysis, fluorescent spectra and TG-DTA spectra. All of above complexes can emit characteristic fluorescence of terbium ions. Fluorescence spectra showed that above Terbium complexes have the order of fluorescent intensity from strongest to weakest as follows: Tb （o-A）3, TbPMA3/4^Tb2 （Ssal）3, Tb （p-A）3, Tb （TMA）, Tb-PMDMBA （PMDMBA= Bisphenol A epoxy acrylate resin modified with pyromellitic dianhydride）. Among all of above complexes, study on synthesis and fluorescent properties of Tb-PMDMBA complex were not reported in the literatures, the complex can emit characteristic fluorescence.2. The parameter n was induced; fluorescent enhanced effects and mechanism of no-fluorescent doped ions were investigated.The results showed that no-fluorescent doped ions can enhance the fluorescent intensity of rare earth complexes, viz. p, values are more then 1, and when \i values gain with molar fraction of doping elements, fluorescent intensity gains. Then, fluorescent intensity weakens gradually after u values exceed optimum. Among these doped complexes of aromatic carboxylic acid, doping elements exist as dissimilar binary nucleus or multi-nucleus, their fluorescent enhancement mechanism belongs to intramolecular energy transfer, viz. "energy concentrating effect"; and then, in B-diketones complexes, doped ions and central ions form complexes with ligands respectively, their fluorescent enhancement mechanism belongs to intermolecular energy transfer, viz. "co-fluorescence effect".3. A series of europium fluorescent agents with red fluorescence and terbium fluorescent agents with green fluorescence were synthesized by in-situ for the first time in the matrix of bisphenol A epoxy acrylate resin （abbreviated EA）, their properties were characterized by FTIR, UV-Vis spectra, fluorescent spectra et al.（1） The doped ternary complexes of europium with TTA and Phen, tetracomplexes of europium with TTA, cry lie acid （or sulfosalicylic acid ） and Phen, complex of europium with benzoic acid and phenanthroline were synthesized in EA. The above fluorescent agents have good tolerated and dispersal stability with the UV-curing resin. They can emit strong characteristic fluorescence of europium ion under ultraviolet radiation, Fluorescent intensity of above fluorescent agents have the order from strongest to weakest as follows: fluorescent agent FL-1 n fluorescent agent FL-IV, fluorescent agent FL- II ^ fluorescent agent FL-III, fluorescent agent FL-VI > fluorescent agent FL- V n fluorescent agent FL-VII -, fluorescent agent FL-V1II?（2） Binary complex of Terbium with sulfosalicylic acid, ternary complex of Terbium with sulfosalicylic acid and trioctylphosphine oxide, binary complex of Terbium with pyromellitic acid, ternary complex of Terbium with pyromellitic acid and trioctylphosphine oxide and binary complex of Terbium with p-aminobenzoic acid were synthesized in EA. The above fluorescent agents have tolerated and dispersal stability with the UV-curing resin. They can emit strong characteristic fluorescence of terbium ion under ultraviolet radiation. The fluorescent intensity of above fluorescent agents have the order from strongest to weakest as follows: fluorescent agents FL- X > fluorescent agents FL-IX> fluorescent agents FL-^ fluorescent agents FL-XIk fluorescent agents FL-XK4. Bisphenol A epoxy acrylate waterborne UV-curing resin modified by maleic anhydride （abbreviated: EB） and low adhesiveness waterborne UV-curing resin （abbreviated: EC） were synthesized. The resins are used as vehicles of inks, which has important environment protective function because the inks are improved from the solvent type of inks to the no-solvent type of inks.Effects of reaction conditions including temperature, time, type and content of catalyzes, type and content of polymerization-retarded on reaction velocity, degree of reaction and loss of double bond were investigated, the optimum conditions of reaction are ascertained.5. UV-curing （and waterborne UV-curing） falsification-resistant inks with red fluorescence and green fluorescence were prepared respectivelyRheology property, steady property, UV-curing property and fluorescent propertyof the inks are good. And effect factors of UV-curing mechanism and UV-curing velocity of inks were investigated.6. Fluorescent quenching effects and mechanism of rare earth fluorescent complexes in polymer-base were investigated for the first timeFluorescent quenching effects on rare earth fluorescent complexes caused by doped elements, type of ligands, type of resins and type of photoinitiators were investigated in the details, and correlative theory was discussed. "Fluorescent protective layer" model was put forward according to type of ligands which include strong electronegativity atoms or not. Fluorescence is safeguarded as "Fluorescent protective layer" which come from hydrogen bonding between strong electronegativity atoms of ligands and hydroyl groups of EA is formed, the fluorescence is quenched when "Fluorescent protective layer" is not formed. Fluorescent quenching effects and mechanism of resins on rare earth fluorescent complexes were investigated according to "static fluorescent quenching". Fluorescent quenching effects and mechanism of photoinitiators on rare earth fluorescent complexes were investigated according to "interfiltering effect".更多还原