发光学报, 2009, 30 (2): 252, 网络出版: 2009-12-30   

三元配合物Eu(BA)3PIP和Eu(BA)3phen的制备与发光性质

Preparation and Fluorescence Properties of Ternary Complexes of Eu(BA)3PIP and Eu(BA)3phen
作者单位
1 长春理工大学 材料科学与工程学院, 吉林 长春130022
2 沈阳东基工业集团有限公司, 辽宁 沈阳110045
摘要
合成了邻菲罗啉(phen)衍生物2-苯基-咪唑并[4,5-f]-1,10-菲罗啉(PIP),并以其为第二配体,苯甲酸(BA)为第一配体,制备出新型稀土铕三元有机配合物Eu(BA)3PIP;在相同条件下,第一配体不变,1,10-菲罗啉为第二配体,还制备出Eu(BA)3phen。采用元素分析、红外光谱、热重和差热分析等技术对合成的配体PIP及配合物Eu(BA)3PIP和Eu(BA)3phen进行了表征。通过发光光谱研究了配合物的发光性质,结果表明第二配体PIP有较大的共轭体系,在紫外光激发下,配合物中的配体可将吸收的能量传递给稀土Eu3+离子,表现出较强的Eu3+离子的特征发射。两种配合物相比,Eu(BA)3PIP的发光强度明显大于Eu(BA)3phen的发光强度,说明适宜的第二配体对配合物有很好的敏化发光作用。
Abstract
Rare earth complex materials have been widely used in cathodoluminescent display phosphor screens, lasers and lamps because their photoluminescence (PL) exhibits high quantum efficiencies and very sharp spectral bands. The luminescence process of the rare earth complex is as follows:the electrons in excited single state of the ligand move to the triplet state by intrasystem relaxation process, followed by the energy transfers from the triplet state of the ligand to the nearest resonance level of the rare earth ion.In the luminescence process, the single state and triplet state can only be used.Theoretically, the internal quantum efficiency can reach 100%, which is four times than that of other fluorescent materials.When europium ion chelates with some organic ligands, such as benzoic acid(BA), the emissions of rare earth Eu3+ ion exhibits highly pure red color and strong luminescence intensity. The intensity of sensitized luminescence of central lanthanide ions in a rare earth organic chelate depends on three factors.Firstly, the suitability of the energy gap between the excited triplet energy level of the ligands and the lowest excited energy level of rare earth ions. Secondly, the rigidity and planarity of the structure of the chelate molecule.Thirdly, the existence of a suitable secondary ligand which may increase the rigidity and the stability of the chelate molecule.In this paper, 1,10-phenanthroline (phen) derivative, 2-phenyl-imidazo [4,5-f] 1, 10-phenanthroline (PIP) were synthesized.With benzoic acid(BA) as the first ligand and PIP as the secondary ligand, a new ternary organic europium complex Eu(BA)3PIP was prepared.In the same condition, with the same first ligand and phen as the secondary ligand, Eu(BA)3phen was also prepared. The structures and compositions of the ligand PIP, Eu(BA)3PIP and Eu(BA)3phen were confirmed by elemental analysis, IR spectra, TG analyses, the fluorescence properties of the two complexes were also studied. Elemental analysis demonstrates that the compositions of the ternary complexes are PIP , Eu(BA)3PIP and Eu(BA)3phen. IR spectra indicate that rare earth Eu3+ ion is coordinated with six oxygen atoms of three benzoic acid ligands and two nitrogen atoms of the second ligand.The emission spectra demonstrate that two kinds of ternary organic europium complex exhibit characteristic fluorescence of rare earth Eu3+ and the second ligand PIP has larger conjugation system, and under UV excitation, energy absorbed by the ligands in the complex can be transfed to the rare earth Eu3+ ion, so that it can emit characteristic luminescence of Eu3+, and the luminescence intensity of Eu(BA)3PIP is obviously higher than that of Eu(BA)3phen. The luminescence of complex was greatly sensitized by appropriate secondary ligand. TG analyses show that the thermal decomposition temperature of Eu(BA)3PIP are higher than that of Eu(BA)3phen. Thus the secondary ligand of 2-phenyl-imidazo [4,5-f] 1, 10-phenanthroline(PIP) obviously enhanced the fluorescent intensity of Eu3+and the thermal stability of europium complex. So, the new ternary organic europium complex of Eu(BA)3PIP is an excellent red-emitting material.

任晓明, 魏长平, 王鹏, 马志鹏, 丛晓庆. 三元配合物Eu(BA)3PIP和Eu(BA)3phen的制备与发光性质[J]. 发光学报, 2009, 30(2): 252. REN Xiao-ming, WEI Chang-ping, WANG Peng, MA Zhi-peng, CONG Xiao-qing. Preparation and Fluorescence Properties of Ternary Complexes of Eu(BA)3PIP and Eu(BA)3phen[J]. Chinese Journal of Luminescence, 2009, 30(2): 252.

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