8-羟基喹啉高分子化及其稀土配合物光致发光的研究
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摘要
本研究首先以聚丙烯酸（PAA）与氯化亚砜作用，生成聚丙烯酰氯，然后与8-羟基喹啉（8HOQ）反应，制备了带有8-羟基喹啉侧基的聚丙烯酸（PAA8q），实现了8-羟基喹啉高分子化；通过PAA8q与稀土元素Eu（Ⅲ）的配位反应，得到了稀土Eu（Ⅲ）－高分子化8-羟基喹啉配合物（Eu-PAA8q），并确定了制备配合物的最佳条件。通过紫外光谱、红外光谱研究了PAA8q的分子组成与结构，以容量法确定了稀土高分子化8-羟基喹啉配合物中Eu（Ⅲ）的含量及配合物的结构，通过荧光光谱法详细研究了稀土配合物的荧光特性及其发光机理。研究结果表明，聚丙烯酰氯与8-羟基喹啉作用，首先发生酯化反应，然后经弗里斯重排反应实现喹啉环上酰基化反应，使8-羟基喹啉高分子化，得率为36.5％，平均每15.6个聚丙烯酸结构单元含有一个8-羟基喹啉分子；8-羟基喹啉的配位能力强，当PAA8q与三氯化铕作用生成配合物时，首先以8-羟基喹啉配位为主，反应最佳条件为PAA8q中8-羟基喹啉的含量与三氯化铕的配比为1:1，pH=7.5，反应温度为45℃，时间为45min；稀土Eu（Ⅲ）－高分子化8-羟基喹啉配合物中，8-羟基喹啉具有较大的共轭体系，容易发生π-π*跃迁而吸收能量，稀土离子Eu（Ⅲ）f*能级与8-羟基喹啉的最低三重态能级相匹配，从而发生从配体8-羟基喹啉的最低三重态能级到稀土Eu（III）离子f* 能级的分子内能量传递，8HOQ具有强的“天线效应”，使配合物的荧光强度较三氯化铕增强了近14倍。
In this investigation, polyacryloyl chloride was prepared by reacting of polyacrylic acid ( PAA) with SOCl2 firstly, then it was used to react with 8-hydroxylquinoline (8HOQ), the PAA containig 8HOQ side groups was synthesized, which is designated as PAA8q, so the incorporating of 8-hydroxylquinoline into macromolecules was realized. The complex of Eu(Ⅲ)- PAA8q was obtained by coordination reaction of PAA8q with rare-earth ion Eu(Ⅲ), the rare-earth—polymer complex the structure and composition of the rare-earth—polymer complex was characterized using FTIR and UV, its content of Eu(Ⅲ) was measured by volumetric method, and its fluorescence character and emission mechanism was studied on details. The results show that the esterifying reaction occurs firstly, in turn the Friess rearrangement reaction takes place and quinoline ring is acylated when polyacryloyl chloride interreacts with 8HOQ, so that the incorporating 8HOQ into macromolecules is realized. The yield of 8HOQ incorporating into macromolecules is 36.5%, and there is one 8-hydroxylquinoline molecule in 15.6 units of PAA on an average. Owing to the stronger coordinating ability of 8-hydroxylquinoline as ligand，the coordination reaction of 8HOQ with Eu(Ⅲ)is predominant over the coordination reaction of -COOH in PAA8q. The optimum reaction conditions for the coordination reaction determined are as follows. The feed ratio of 8HOQ in PAA8q to EuCl3 is 1:1, pH is 7.5, the reaction temperature is 45℃, and the reaction time is 45 min. The complex of Eu(Ⅲ)- PAA8q has stronger ability of absorbing energy because of great conjugate system of 8-hydroxylquinoline molecule and easieness of π-π* transition. Besides, the f* energy level of ion Eu(Ⅲ) is matchable with the lowest energy level of triplet state of 8-hydroxylquinoline, and the intramolecular energy transfer occurs from 8-hydroxylquinoline to Eu(Ⅲ) easily, i.e. 8-hydroxylquinoline is called to have ‘aerial effect’, so that The complex of Eu(Ⅲ)- PAA8q has stronger fluorescence emission, and its intensity of fluorescence emission is 14 times stronger than EuCl3.
In this investigation, polyacryloyl chloride was prepared by reacting of polyacrylic acid ( PAA) with SOCl2 firstly, then it was used to react with 8-hydroxylquinoline (8HOQ), the PAA containig 8HOQ side groups was synthesized, which is designated as PAA8q, so the incorporating of 8-hydroxylquinoline into macromolecules was realized. The complex of Eu(Ⅲ)- PAA8q was obtained by coordination reaction of PAA8q with rare-earth ion Eu(Ⅲ), the rare-earth—polymer complex the structure and composition of the rare-earth—polymer complex was characterized using FTIR and UV, its content of Eu(Ⅲ) was measured by volumetric method, and its fluorescence character and emission mechanism was studied on details. The results show that the esterifying reaction occurs firstly, in turn the Friess rearrangement reaction takes place and quinoline ring is acylated when polyacryloyl chloride interreacts with 8HOQ, so that the incorporating 8HOQ into macromolecules is realized. The yield of 8HOQ incorporating into macromolecules is 36.5%, and there is one 8-hydroxylquinoline molecule in 15.6 units of PAA on an average. Owing to the stronger coordinating ability of 8-hydroxylquinoline as ligand，the coordination reaction of 8HOQ with Eu(Ⅲ)is predominant over the coordination reaction of -COOH in PAA8q. The optimum reaction conditions for the coordination reaction determined are as follows. The feed ratio of 8HOQ in PAA8q to EuCl3 is 1:1, pH is 7.5, the reaction temperature is 45℃, and the reaction time is 45 min. The complex of Eu(Ⅲ)- PAA8q has stronger ability of absorbing energy because of great conjugate system of 8-hydroxylquinoline molecule and easieness of π-π* transition. Besides, the f* energy level of ion Eu(Ⅲ) is matchable with the lowest energy level of triplet state of 8-hydroxylquinoline, and the intramolecular energy transfer occurs from 8-hydroxylquinoline to Eu(Ⅲ) easily, i.e. 8-hydroxylquinoline is called to have ‘aerial effect’, so that The complex of Eu(Ⅲ)- PAA8q has stronger fluorescence emission, and its intensity of fluorescence emission is 14 times stronger than EuCl3.
引文
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[3] 黄春辉，稀土配位化学，北京：科学出版社，1999，363-380
[4] 杨迟，杨燕生.发光镧系超分子的设计及应用[J].大学化学，1995，10（1）：6-10
[5] 常文保，李克安.简明分析化学手册.北京：北京大学出版社，1981，256-259
[6] 朱淬砺.药物合成反应. 北京：化学工业出版社，1985，395-398
[7] 张颂培，刘英俊，张培至等. 农膜荧光转光技术进展[J].现代塑料加工应用，1999，11（1）:58-60
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[9] Yuji Hamada, Hiroshi Kanno, Takeshi Sano et al. Organic light emitting diodes using a gallium complex[J]. Appl.Phys.Lett,1998,72(7):756-758
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[11] M Zheng, F L Bai, et al. Synthesis and characterization of a high-emitting alternating copolymer[J]. J Polym Sci, Part A:Polym Chem,1999,37:2587
[12] 李文连. 稀土有机配合物的发光研究的进展[J]. 化学通报，1991，7（1）：1-8
[13] 杨明山. 高光效膜的制备与应用研究[J].塑料科技，1995（4）：23-25
[14] V B No, S N Krivstsova, N E Petrova, et al. Method of Producing Acryloyl Chloride[P].SU 1595835
[15] J.E Meinhardt. Determination of sub-nanomolar levels of iron using flow injection with chemiluminescence detection[J].Science,1948,110:387
[16] H.P Gregor, M Taifer. Ind Chem,1952,44:2834
[17] Von Lillin. AngewChem,1954,66:649
[18] G Manecke. Rapid precipitation of trace metals from high saline matrices
by Poly-5-vinyl-8-hydroxyquinoline[J]. Makromol Chem,1970,133:83
[19] J.R Parrish. Vinyl polymer agglomerate based transition metal cation chelating ion-exchange resin containing the 8-hydroxyquinoline functional[J].Chem Ind,1956,137:92
[20] G K J Gibson, D I Packham. JApplChem,1966,16:50
[21] H Robert, Herrocks, C Eugene. Principles of Aquatic Chemistry[J].Poly Sci,1963,1:3655
[22] F Vernon, K.M Nyo. SAnal Chim Acta,1977,93:203
[23] M.S.Weaver, D.G.Lidzey, M.A.Pavier. Organic light emitting diodes based on Langmium-Blodgett films containing rare earth complexes[J]. Synth.Met,1996,76:91-93
[24] F.巴索罗，R.蒋逊著.宋银柱，王耕霖等译. 配位化学. 北京：北京大学出版社，1980：2-5
[25] 游效曾编著. 配位化合物的结构和性质. 北京：科学出版社，1992：87-96
[26] S I Weissan. Intramolecular energy transfer-the fluorescence of complexes of europium[J]. J chem. phys, 1942, 10: 214-217
[27] G A Grosby. Luminescent organic complexes of the rare earth metals[J]. Mol Cryst, 1966, 1(1): 6-10
[28] S P Sinha, C N K In Rao，J P Ferraro. Spectroscopy in inorganic chemistry[J]. Vo12, Academic Press, New York,1971
[29] Albin Michael, D Jr Horrocks William. Quantitative correlation between the total charge on the ligands and the 7F0→5D0 transition frequency in Europium(Ⅲ) complexes[J]. Inorg chem., 1985, 24(6):895-900
[30] 苏锵. 稀土有机化合物的发光与能量传递[J].发光学报，1986，7（1）:1-5
[31] 李文连，王庆荣，卫革东等.含稀土有机配合物的光能转换蔬菜大棚膜的研究[J].稀土，1993，14（1）：25-28
[32] 杨燕生.中国稀土学会第二届学术年会论文集[J].1992，2分册上：153-154
[33] 足立吟也.日本特许公报.1973，72（290）：994
[34] 孙刚，李文连，虞家琪. 有机材料TB(ACAC)3Phen为发射层的绿色发光二极管[J]. 中国稀土学报，1996，14：220-223
[35] Y Okmaoto, Y Ueba, N F Dzhanibekov, et al. Rare earth metal containing polymer 3 Characterization of ion-containing polymer structures using rare earth metal fluorescence probes[J]. Macromolecules,1981,14(1):17-22
[36] Wolff N E, Pressley R J. Optical masser action in Eu3+containing orgnic Matrix. Appl Phys Lett, 1963, 2(8): 152~154
[37] J. Kido, H. G. Brittain, S. Paoletti, Investigation of Ion Binding Properties of Synthetic Polyelectrolyte Using a Terbium(Ⅲ) Probe: Elucidation of the Number of Coordinated Water Molecules on Metal Polyelectrolyte Complexes[J]. Macromolecules, 1988, 21: 1872-1875
[38] 凌启淡，章文贡. 稀土高分子荧光材料研究综述[J]. 高分子通报.1998, (3): 48-58
[39] G.Gustafasson, Y.gao, G.M.Treacy, A.J.Heeger. Flexible light emitting diodes made from soluble conducting polyme[J]r. Nature 1992,357:477-479
[40] 李健宇，张颂培，曾红.稀土配合物光转换剂研究的现状与展望[J].现代化工，1998（12）：10-11
[41] 杨武，陈森，高锦章等.镧系配合物的荧光光谱[J].光谱学与光谱分析，1999，19（2）：227-229
[42] A.J.heeger, Kivelson, S.Schrieffer. Solitons in conducting polymer[J]. Rev.Mod.Phys. 1998,60:781-850
[43] 王海滨，刘军，张迎等. 稀土应用的概况和今后开发重点的建议[J].山东化工，1999（4）：30-34
[44] 李健宇，张颂培，曾红.稀土配位化合物光转换剂的设计[J].中国塑料，1999，13（1）：44-47
[45] 王则民，傅楚瑾，曹锦荣等.稀土转光农膜的光色效应研究[J]. 中国塑料，1999，13（12）：21-23
[46] Y.Yang, A.J.Heeger. Polyaniline as transparent electrode for polymer light
emitting diodes lower operating voltage and high efficiency[J]. Appl.Phys.lett,1994,64:1245-1247
[47] 何晓东，冯嘉春.稀土有机光转换剂技术概述[J].兰化科技，1997，15（3）：202-204
[48] 雷光东，卢志云，朱卫国等.有机荧光防伪材料的制备[J].化学研究与应用，1999，11（3）：208-211
[49] 田君，尹敬辉.稀土荧光防伪油墨的制备[J].精细化工，1999，16（2）：31-33
[50] 李斌，马文阁，张洪杰等.铕三元配合物红色薄膜电致发光器件[J].科学通报1997（12）：45-48
[51] 钱东金，杨孔章.稀土螯合物发光体LB膜的研究（Ⅰ）[J].物理化学学报，1993，9（12）：148-150
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