RE(POA)3phen配合物的合成、表征及荧光性能

合成了以稀土离子Sm³⁺、Eu³⁺、Tb³⁺、Dy³⁺及Tb³⁺为发光中心,以苯氧乙酸(HPOA)和邻菲罗啉(phen)为配体,掺杂La³⁺、Gd³⁺、 Y³⁺的7种稀土配合物, 对配合物进行了C、H、N元素分析、稀土络合滴定、红外光谱、紫外光谱和发光光谱的研究。结果表明配合物的组成分别为SmL₃L'·1/2H₂O,EuL₃L'·1/2H₂O,TbL₃L'· 1/2H₂O,DyL₃L'·1/2H₂O,掺杂配合物组成分别为Tb_0.5Gd_0.5L₃L'·1/2H₂O,Tb_0.5Y_0.5L₃L'·1/2H₂O,Tb_0.5La_0.5L₃L'·1/2H₂O(L=C₆H₅OCH₂COO^-, L'=phen)。配合物中的稀土离子与苯氧乙酸中羧基的一个氧原子和苯氧基的氧原子配位,与邻菲罗啉中的两个氮原子配位成键;荧光光谱表明,铽三元配合物的发射强度要远大于其它三元配合物的发光强度,掺杂发光惰性稀土离子La³⁺、Gd³⁺、Y³⁺的铽配合物中,Y³⁺掺杂配合物的发光强度有所增强。

Synthesis,Structure Characterization and Fluorescence Properties of the Solid Complexes of Rare Earth with 1,10-Phenanthroline and Phenoxyacetic Acid

Seven complexes of rare earth (Ln=Sm,Eu,Tb,Dy)and Tb3+ doped with RE3+ (La3+, Gd3+, Y3+ )with phenoxyacetic acid ( HPOA ) and 1, 10-phenanthroline were synthesized. Their elemental analysis and rare earth complexometic titration were determined,the results showed that the chemical formulas were SmL3L'·1/2H2O,EuL3L'·1/2H2O,TbL3L'· 1/2H2O,DyL3L'·1/2H2O,Tb0.5Gd0.5L3L'·1/2H2O,Tb0.5Y0.5L3L'·1/2H2O,Tb0.5La0.5L3L'·1/2H2O(L=C6H5OCH2COO-, L'=phen).IR spectra, UV spectra and fluorescence spectra were studied. The results indicated that the rare earth ions are bounded with the oxygen atoms of phenoxyacetic acid and phenoxy, and with the N atoms of 1,10-phenanthroline. Fluorescence spectra of the complexes are determined at room temperature, the terbium complex showed that there is a characteristic excitation peak,which is a wide band from 280 to 380 nm, and a maximum peak at 331 nm. For europium complex, the band is from 280 to 370 nm and with a maximum peak at 348 nm.For dysprosium and samarium complexes, the bands are from 290 to 350 nm and 320 to 370 nm,the maximum peaks at 333 nm and 354 nm,respectively.The characteristic excitation peaks are assigned to the ligands metal energy transfer band. So, 331,348,333 and 354 nm were chosen as excitation wavelength to measure the fluorescence spectra of terbium,europium,dysprosium and samarium complexes,respectively. The intensity of terbium complex is the strongest, europium complex is second and samarium is the weakest.It was shown that the lowest excitation state energy level of Tb3+ ion matches well with the triplet state energy of the ligand phenoxyacetic acid and phenanthroline each other,the absorbing energy of the ligands may effectively transferred to Tb3+ion. The fluorescence intensity of terbium complex is enhanced after doping Y3+ ion.