【作者】 安晓萍；

【导师】 赵永亮；

【作者基本信息】 内蒙古大学 ， 无机化学， 2004， 硕士

【摘要】 本文首次合成并表征了稀土高氯酸盐与冠醚、对苯二甲酸的三个系列十五种固态配合物。经元素分析、摩尔电导及差热-热重分析，结果表明其组成分别为：铕系列Eu₂LL′₂（ClO₄）₄·6H₂O；EuREL L′₂（ClO₄）₄·nH₂O{RE=La（n=6）；RE=Gd，Y（n=9）}：铽系列 Tb₂L L′₂（ClO₄）₄·12H₂O；TbREL L′₂（ClO₄）₄·nH₂O{RE=La（n=9）；RE=Gd，Y（n=12）}；Tb₂LL″₂（ClO₄）₄·12H₂O；TbGdL L″₂（ClO₄）₄·12H₂O；铕铽系列(Eu_xTb_1-x)₂L L′₂（ClO₄）₄·nH₂O（x=0.1，0.3，0.5，0.7，0.9；n=12-6x）。（L=（?）；L=（?）；L″=（?））。在这些配合物中，与冠醚分子的氧原子直接配位的稀土离子有Eu³⁺离子和La³⁺离子，而Gd³⁺、Y³⁺和Tb³⁺则与3个水分子的氧原子配位，水分子再与冠醚分子的氧原子形成氢键。红外光谱及摩尔电导率表明，对苯二甲酸的羧基与稀土离子发生了配位作用；四个无机平衡阴离子ClO₄^-中，两个在内界，两个在外界。配合物的荧光光谱和荧光寿命测定表明，相同配体的铽系列配合物的荧光强度明显强于铕系列，荧光寿命也长于铕系列；异核稀土配合物的荧光强度和荧光寿命与相应同核稀土配合物相比，均有不同程度提高；铕-铽配合物中，Tb³⁺对Eu³⁺的荧光有敏化作用，而Eu³⁺对Tb³⁺却有很强的猝灭作用；不同冠醚配体的稀土配合物的荧光强度不同。更多还原

【Abstract】 Three series of fifteen solid complexes of rare earth perchloratewith crown ethers and p-phthalic acid have been synthesized andcharacterized first time in this article. Their elemental analysis, rareearth complexometry, molar conductives and TG-DTA studies indicate that the complexes have the composition of Eu2LL’2(ClO4)4 6H2O; EuRELL’2(ClO4)4 nH2O{RE=La(n=6); RE=Gd, Y(n=9)}; Tb2LL’ 2(C1O4)4- 12H20; TbRELL’ 2 (ClO4)4 nH20 {RE=La(n=9) ;RE=Gd, Y(n=12)} ; Tb2LL" 2(C104)4 12H20, TbGdLL" 2(Cl04)4 12H20; (EuxTb1-x) 2LL’ 2C104) 4 nH20 (x=0. 1, 0. 3, 0. 5, 0. 7, 0. 9; n=12-6x). (L= respectively. In theserare earth complexes, La3+ ion and Eu3+ion coordinate with oxygen atoms of crown ethers molecules directly, but Gd3+ Tb3+ and Y3+ ions coordinate to oxygen atom of three water molecules which form hydrogen bonds with oxygen atom of crown ethers;IR spectra and molar conductives studies indicate that p-phthalic acid is bounded with RE (III) ion;Two inorganic anions ClO4- among the four ClO4- are coordinated with the rare earth ionsand the other two doesn’t. Fluorescence spectra and fluorescence lifetimes show that the fluorescent intensity and lifetime of a series of terbium complexes are higher than the series of europium’ s when they have the same ligands. There are better fluorescent intensity and lifetime of heteronuclear rare earth complexes than homonuclear rare earth complexes. The fluorescence emission intensity of Eu3+ ion are raised by Tb3+ in Eu3+ -Tb3+ compounds and intensity of Tb3+ ion are quenced by Eu3+ ion. The fluorescence intensity are different in heterogeneous crown rare earth coordination compounds.更多还原