对甲苯基苯乙烯基亚砜稀土高氯酸盐体系中Tm^(3+)→Eu^(3+)的荧光增强效应

Study on Fluorescence Enhance Effect of Thulium Perchlorate to Europium Perchlorate in Styryl P-Tolyl Sulfoxide

合成并表征了六种不同掺杂比例稀土高氯酸铕掺铥与对甲苯基苯乙烯基亚砜的固态配合物。经元素分析确定了配合物的组成为:(EuxTm1-x)(ClO4)3.L7(x=1.000,0.999,0.995,0.990,0.950,0.900;L=C6H5CH=CHSOC6H4CH3)。配合物的红外光谱表明,配体通过亚砜基氧原子与稀土离子配位,烯键未参与配位。在丙酮溶液中测定的摩尔电导率表明,配合物为1∶2型电解质,三个ClO4-无机抗衡阴离子,其中一个在内界,两个在外界。配合物的荧光发射光谱中出现了比磁偶极跃迁(5D0→7F1)强的电偶极跃迁(5D0→7F2),表明配合物不存在反演中心。掺杂配合物的荧光光谱表明,将千分之一的铥掺入后,铕离子的发光增强增加到111%。

Six-different proportional mixed complexes（Eu^3＋ mixed by Tm^3＋） of rare earth perchlorate with the ligand（L） have been synthesized and characterized.By elemental analysis,the compositions of the complexes were suggested as（EuxTm1-x）（ClO4）3（L7（x=1.000,0.999,0.995,0.990,0.950,0.900;L= C6H5CH=CHSOC6H4CH3） respectively.IR spectra studies indicated that styryl p-tolyl sulfoxide（L） bonded with RE3＋ by the oxygen atom in sulfinyl group while vinyl did not.The molar conductivities in acetone solution indicated that one of the three inorganic anions ClO4-is coordinated with RE3＋.Fluorescence spectra of the europium complexes exhibit Eu3＋ characteristic red emission,when excitation light was fixed at 393 nm.The fluorescent intensity of electric dipolar 5 D0→7F2 transition is stronger than that of the magnetic dipolar 5 D0→7F1 transition.This phenomenon suggests the europium ion is located at an asymmetry environment and the complex has not a center of symmetry.Comparing the fluorescent spectrum of the simple europium complex with those of mixed coordination compounds,one can find that the thulium ions have a sensitization effect on the fluorescence of the europium ions.And sensitization effect is the strongest when the ratio of thulium ions and europium ions is 0.001∶0.999.