光谱学与光谱分析, 2011, 31 (11): 2973, 网络出版: 2011-12-22  

新型稀土铕, 铽β-二酮配合物的合成与荧光性质

Synthesis and Fluorescence Property of Novel Rare Earth Europium, Terbium Complexes with β-Diketone
作者单位
长春理工大学材料科学与工程学院, 吉林 长春130022
摘要
采用克莱森缩合反应合成了一种新型的β-二酮化合物1-(4-氨基苯)-4,4,4-三氟丁烷-1,3-二酮(p-NBFA)。 以其为第一配体, 邻菲咯啉(phen)为第二配体, 合成出新型Eu(Ⅲ), Tb(Ⅲ)三元配合物。 通过元素分析确定了配合物的组成为Eu(p-NBFA)3phen和Tb(p-NBFA)3phen。 红外光谱的分析表明p-NBFA中的氧原子以及phen中的氮原子与稀土离子进行了配位。 紫外光谱表明第一配体p-NBFA为能量传递的主体, 第二配体phen起协同作用。 通过荧光光谱研究了配合物的发光性质, 结果显示在Tb(p-NBFA)3phen中, 除Tb3+的特征发射外, 还可以观察到470 nm的发射, 进一步的研究表明, 此处发射为配体p-NBFA的发射, 这是由于配体的能级与Tb3+的发射能级较近, 产生了逆传能过程。 而在Eu(p-NBFA)3phen的发射谱中, 均表现出稀土离子的特征发射, 且发光强度较大, 说明配体的能级与Eu3+的发射能级比较匹配。
Abstract
A novel β-diketone 1-(4-aminophenyl)-4,4,4-trifluorobutane-1,3-dione(p-NBFA) was synthesized by Classical claisen condensation reaction. With p-NBFA as the first ligand and 1,10-phenanthroline(phen) as the secondary ligand, two new rare earth Eu(Ⅲ), Tb(Ⅲ) ternary complexes were prepared. Elemental analysis demonstrated that the compositions of the complexes were Eu(p-NBFA)3phen and Tb(p-NBFA)3phen. IR spectra indicated that rare earth ions were coordinated with oxygen atoms of the first ligand and two nitrogen atoms of the secondary ligand. UV spectra showed that the main absorption was from the first ligand in the complexes, the secondary ligand was acted as the synergistic coordination. Fluorescence spectra demonstrated that the emission intensity of Eu(p-NBFA)3phen was obviously stronger than that of Tb(p-NBFA)3phen. Further investigation showed that the emission intensity was influenced by the matching situation of energy level between the triplet state of ligand and the emission energy of rare earth ion. In Tb(p-NBFA)3phen, due to that the triplet state energy level of p-NBFA was too near to the energy level of 5D4, then the energy transfered back to the ligand, most of the excitation energy was consumed, so the terbium complex showed lower luminescence intensity and competitive luminescence of p-NBFA also appeared. In Eu(p-NBFA)3phen, the energy level difference was well matched and the emission of europium complex was characteristic and high.

任晓明, 魏长平, 程果, 吕景文. 新型稀土铕, 铽β-二酮配合物的合成与荧光性质[J]. 光谱学与光谱分析, 2011, 31(11): 2973. REN Xiao-ming, WEI Chang-ping, CHENG Guo, L Jing-wen. Synthesis and Fluorescence Property of Novel Rare Earth Europium, Terbium Complexes with β-Diketone[J]. Spectroscopy and Spectral Analysis, 2011, 31(11): 2973.

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