镧系金属-β-二酮-邻菲罗啉类三元螯合物的合成、表征及发光性能的研究
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摘要
有机电致发光材料是近年来国际上一个非常热门的研究领
域。本文较详细的综述了有机电致发光材料的研究进展。在众多
的有机电致发光材料中，调系金属鳌合物是一类具有特殊发光性
能和物理性质的电致发光材料。因它们具有荧光量子效率高、发
光谱带窄、色度纯等优点，对它们的研究越来越受到人们的重视。
我们用二氯亚识、苯甲酸、l一苯基3一甲基巧此地批酮等原料
合成了第一配体l一苯基上一甲基4一苯甲酚基巧I 哩琳酮
（HPMBP人 l，10早菲罗琳经硝化、还原、与丙烯酚氯酚化合
成了第二配体 5一丙烯酸胺一l，10一邻菲罗琳（5－a－l，10－phen）；并
将它们分另与调系金属离子Ld”、Pr‘”、Nd’”、Eu‘“、Dy’”、Er’”、
Tin叶、Ybn在乙醇一水溶液作反应，合成了八种斓系金属下一二酮一
邻菲罗琳衍生物H元固态螫合物；这八种螫合物和5一丙烯酚胺l，
10运菲罗琳均为未见文献报道的新化合物。通过红外、紫外、核
磁、质谱等分析测试手段对它们进行了系统、严格的分析和表征，
确证了它们 的结构，其通式为 Ln（PMBP）。（5－a－l，10－phen）
（Lfl＝L。，pf，Nd，Elf，Dy，Ef，Tin，Yb）；测定了该系列鳌合
物的摩尔电导率、溶解性和热稳定性等物理性质；研究了三元叠
合物的荧光激发和发射光谱，发现它们均能吸收紫外光，发射蓝
紫色可见光，与自由配体相比，通过斓系金属离子的配位，配体
的荧光强度得到加强，其中La、Nd、Eu、Dy这四种螫合物的荧
光强度显著增强，半峰竞变窄，即提高了配体的单色纯度；根据
它们的光致发光性能（荧光光谱人探讨了它们作为电致发光材料
的应用前景，它们可能是一种具有优良传输性能的发光材料，若
用于电致发光器件中，能够作为发光层材料，并发射蓝光。
Organic electroluminescent (OEL) materials have become a
new and fascinating area of research in recent years. The research
status and development of organic electroluminescent materials are
reviewed in detail in this paPer. Lanthanide metal chelates are a kind
of electroluminecent materials with special light and physical
properties among many OEL materials. They have received more and
more attention from many investigators for high fluorescence
efficiency, narrow bandwidth, good purity of light.
We have prepared the first ligand, l-benZyl-3-
methyl-4(benzoyl-5-pyrazolone using dichloro ed for all all
lH methyl-5-pyrazolone .From l,l0-phenallthroline, we have
prepared 5-acrylamido-l, l0- phenanthroline (5-a-l, l0-phen),the
second ligand, through nitfation, reduction and acylation reaction
with acryloyl chloride. Then we have prepared their eight lanhanide
metal derivatives ternary solid complexes. They and
5-acrylamido-l,10-phenanthrolin there are nine novel comPounds
which have not been reported so far. All these compounds have been
identified through IR, UV lH NMR, and MS. These complexes all
have the comPosition of Ln(PMBP)3(5-a-l, l0-phen) (Ln=La, Pr, Nd,
Eu, Tm, Yb); We have determined the physical properties about the
molar conductivity solubility and thermal stability of the complexes;
We have studied on the fluorescence excitation and emission
spectrum of the temary solid complexes and found that alI of them
absorb ultraviolet and emit violet visible ligh and their stfCngth, is
obviously strengthened,especial that of La, Nd, Eu, Dy chelates. The
bandwidth is narrower, that is that the purity of light is high.
According to photoluminescence (fluorescence spectrum), we have
discussed their electroluminecence and calculated they are a kind of
emitting-light materials with transport properties. If they are used in
EL devices they can be used emitting layer materials and emit violet
light.
域。本文较详细的综述了有机电致发光材料的研究进展。在众多
的有机电致发光材料中，调系金属鳌合物是一类具有特殊发光性
能和物理性质的电致发光材料。因它们具有荧光量子效率高、发
光谱带窄、色度纯等优点，对它们的研究越来越受到人们的重视。
我们用二氯亚识、苯甲酸、l一苯基3一甲基巧此地批酮等原料
合成了第一配体l一苯基上一甲基4一苯甲酚基巧I 哩琳酮
（HPMBP人 l，10早菲罗琳经硝化、还原、与丙烯酚氯酚化合
成了第二配体 5一丙烯酸胺一l，10一邻菲罗琳（5－a－l，10－phen）；并
将它们分另与调系金属离子Ld”、Pr‘”、Nd’”、Eu‘“、Dy’”、Er’”、
Tin叶、Ybn在乙醇一水溶液作反应，合成了八种斓系金属下一二酮一
邻菲罗琳衍生物H元固态螫合物；这八种螫合物和5一丙烯酚胺l，
10运菲罗琳均为未见文献报道的新化合物。通过红外、紫外、核
磁、质谱等分析测试手段对它们进行了系统、严格的分析和表征，
确证了它们 的结构，其通式为 Ln（PMBP）。（5－a－l，10－phen）
（Lfl＝L。，pf，Nd，Elf，Dy，Ef，Tin，Yb）；测定了该系列鳌合
物的摩尔电导率、溶解性和热稳定性等物理性质；研究了三元叠
合物的荧光激发和发射光谱，发现它们均能吸收紫外光，发射蓝
紫色可见光，与自由配体相比，通过斓系金属离子的配位，配体
的荧光强度得到加强，其中La、Nd、Eu、Dy这四种螫合物的荧
光强度显著增强，半峰竞变窄，即提高了配体的单色纯度；根据
它们的光致发光性能（荧光光谱人探讨了它们作为电致发光材料
的应用前景，它们可能是一种具有优良传输性能的发光材料，若
用于电致发光器件中，能够作为发光层材料，并发射蓝光。
Organic electroluminescent (OEL) materials have become a
new and fascinating area of research in recent years. The research
status and development of organic electroluminescent materials are
reviewed in detail in this paPer. Lanthanide metal chelates are a kind
of electroluminecent materials with special light and physical
properties among many OEL materials. They have received more and
more attention from many investigators for high fluorescence
efficiency, narrow bandwidth, good purity of light.
We have prepared the first ligand, l-benZyl-3-
methyl-4(benzoyl-5-pyrazolone using dichloro ed for all all
lH methyl-5-pyrazolone .From l,l0-phenallthroline, we have
prepared 5-acrylamido-l, l0- phenanthroline (5-a-l, l0-phen),the
second ligand, through nitfation, reduction and acylation reaction
with acryloyl chloride. Then we have prepared their eight lanhanide
metal derivatives ternary solid complexes. They and
5-acrylamido-l,10-phenanthrolin there are nine novel comPounds
which have not been reported so far. All these compounds have been
identified through IR, UV lH NMR, and MS. These complexes all
have the comPosition of Ln(PMBP)3(5-a-l, l0-phen) (Ln=La, Pr, Nd,
Eu, Tm, Yb); We have determined the physical properties about the
molar conductivity solubility and thermal stability of the complexes;
We have studied on the fluorescence excitation and emission
spectrum of the temary solid complexes and found that alI of them
absorb ultraviolet and emit violet visible ligh and their stfCngth, is
obviously strengthened,especial that of La, Nd, Eu, Dy chelates. The
bandwidth is narrower, that is that the purity of light is high.
According to photoluminescence (fluorescence spectrum), we have
discussed their electroluminecence and calculated they are a kind of
emitting-light materials with transport properties. If they are used in
EL devices they can be used emitting layer materials and emit violet
light.
引文
[1]A.A.Bergh,P.J.Dean,Light-emittingDiodes,ClarendonPress,Oxford,(1976):526.
[2] D.D.C.Bradley, Synth. Met., 54(1993): 401.
[3] C.W.Tang,S.A.V.Slyke,Appl.Phys.Lett.,51(1987):913.
[4]C.Adachi,S.Tokito,T.Tsutsui et al.,Jpn.J.Appl.Phys.,27 (1988):L7113.
[5] J.H.Burroughes, D.D. C. Bradley, A. R. Brown, R.N.Marks, K. Mackey, R.H. Friend, P. L. Burn, A.B. Holmes.,Nature, 347(1990):539.
[6]J.L.Segura.,The chemistry of electroluminescent organic materials, Acta Polym.,49(1998): 319～344.
[7] 李文连，有机EL进展，液晶与显示，11（3）(1996)：218～226。
[8] Y. Hamade, IEEE Transaction on electron Devices, 44(8) (1997)：1208.
[9] S.A.V.Slyke,C.H.Chen,C.W.Tang,Organic Electrluminecent devices with improved stability, Appl. Phys. Lett., 69(15)(1996):2160～2162.
[10] N. Masakatsu, K.Noriko, JP 11-54283(99 054 283).
[11] I.Koan, Jpn. Kokai Tokkyo Kohn, JP 07-26254(95 026 254 ).
[12] 张晓宏，吴世康等，几种吡唑啉酮衍生物的光致发光和电致发光特性研究，化学学报，58（3）（2000）：293～296。
[13] C. P. Lin, et al. Jpn.Polym.Res., 2(3) （1995）: 133～138.
[14] 赵云祥， 闻天泽，分析化学中的配位化合物， 北京大学出版社， (1986):275～281。
[15] T. Nakocyama, T.Tsutsui, Enhancement in I-D optical resonator devices with organic films ,Synth. Met., 91（1997）: 58.
[16] 朱卫国，苑同锁， 卢志云，谢明贵，材料导报，1(2000):50～54
[17] J.Kido, et al, Chem. Lett. (1991): 267
[18] Y. Hamada, T. Sano, M. Fujita, etc.Organic Electroluminecent Devices with 8-hydroxyquinoline Derivative-Metal Complexes as an Emitter, Jpn.J. Appl. Phys., 32(4A)（1993）: L514～515.
[19] A.Fujii, M.Yoshida,et al, Color-variable Electrluminescent diode with Single quantum Well Structure Utilizing 8-hydroxqinolineAluminum and Aromatic Diamine,Jpn.J.Appl.Phys.,34(48)( 1995): L499.
[20] J. Kido, K. Nagai, Y. Okamoto,etc. Chem. Lett., (1991):1267.
[21] M. Granstr?m and O. Ingan?s, White light emission from a polymer blend light emitting diode,Appl. Phys. Lett.,68(2)( 1996):147～149.
[22]K.Okada,M.Uekawa,Y.F.Wang,etc.,T.Nakaya,Chem.Lett.,(1998):80.
[23] M. Vekawa, Y. Miyamoto, H. Ikeda, Kaifu, T. Nakaya, Bull. Chem. Soc. Jpn.,71(1998): 2253～2258.
[24] Y. Hamada, T. Sano, M. Fujita,etc.,Blue Electroluminecence in Thin Film of Azomethin-Zinc Complexes, Jpn. J. Appl. Phys. 32(4A) (1993):L511.
[25] J. Kido, K. Okuyama, K. Nagai,White light-emitting orgnic electrolumineslentt devices using the poly(N-vinylcarbazole) emitter layer doped with three fluorescent dyes,Appl. Phys. Lett., 64(7) (1994):815～817.
[26] Y. Hamada, T. Sano, M. Fujita, T. Fujii, Y. Nishio and K. Shitata, White-light Emitting Material for organic eledtroluminescentt Devices,Jpn. J. Appl. Phys. 35(10B)(1996):L1339～L1341
[27] J. Kido, Y. Lizumi,Fabrication of highly efficinent organic electrouminescent devices,Appl. Phys. Let., 73(19) (1998): 2721～2723.
[28] J.Kido, K.Hongawa, K.Okuyama, K.Nagai, Bright blue electro- luminescente from poly(N-vinylcarbazole), Appl. Phys. Lett.63 (19) (1993):2627.
[29]I.Sokolik, Z.Yang, F.E.Karasz, D.C.Morton, Blue-light electro- luminescente from p-phenylene vinelene-based copolymers Appl. Phys., 74(1993):3584.
[30] Y.Ohamai M.Uchida,K.Nuro,K.Koshino,Solid State Com.,80(1991): 605.
[31] N. C.Greenham, S.C. Moraft, D.D.C.Bradley et al. Nature, 365(1993):628.
[32] G.Emmanuette, J.Michel, C.Sentein, et al. Synth. Metals, 81(1996):197.
[33] J. Bharathan and Y. Yang , Polymer electroluminescent devices processed by inject printing:I.Polymer Light-emitting Logo ,Appl. Phys. Lett., 72(1998): 2660.
[34]Hong Meng, Wang-Lin Yu, Wei Huang, Facil Synthetic Route to a Novel Electroluminescent Polymer Poly(p-phenylenevinylene) Containing a Fully Conjugated Aromatic Oxdiazole Side Chain, Macromolecules, 32(1999):8841.
[35]D. Mikael Johansson, Gordana Srdanov, Gang Yu et al. Synthesis and Characterization of Highly Soluble Phenyl-Substitute Poly(p-phenylenevinylenes), Macromolecules, 33(2000):2525～2529.
[36] Ching-Lan Chao, Show- An Chen, White light emission from exciplex in a bilayer device with two blue light-emmitting polymers, Appl. Phys.Lett.73(4)( 1998): 426～428.
[37]Xue Zhang, A.S., Shetty, S.A. Jenekhe, Electroluminescence and Ptotophysical Properties of Polyquinolines, Macromolecules, 32(1999): 7422
[38] T. Ohnisti, S. Doi, Y. Tsuchida, T. Noguchi, IEEE Transaction on Electron Devices, 44(8)( 1997): 1253～1257.
[39] 曹红，高希存，黄春辉等，比唑啉衍生物作为空穴传输层在电致发光材料中的应用，感光科学与光化学，17（4）（1999）：357～359。
[40]Kathirgamanathan, Poopathy. Electroluminescent materials. WO 00 26,323.
[41]Yamaguchi, Takahito; Ota, Masabumi, etc. Org.EL.element. JP 05,17,766[93,17,766].
[42]Hu,Mai-Liu; Huang,Zhenyan; Cheng,Yaqian, etc.Crystal Structure and fluorescence spectrum of the complex Eu(TTA)3phen, Chin. J. Chem. 17(6)(1999):637～643.
[43] 李文连，有机电致发光发射材料用金属络合物研究，功能材料，28(2)(1997)：109～114。
[44] Michacl D.,McGehee,Bergstedt,Troy,etc.,Narrow bandwith luminescence from blends with energy transfer from semiconducting conjugated polymers to europium complexes., Adv. Mater. 11(16)(1999): 1349～1354.
[45]Noriyuki Takada, Tetsuo,Tsutsui and Shogo Saito., Strongly Directed Emission from Controlled-Spontaneous-Emission EL Diodes with Europium Comolex as an Emitter. Jpn.J.Appl.Phys.,Part 2,33(6B)(1994),L863～866.
[46]S., Takeski; Fujita, Masayuki,etc.,Novel europium complex for EL devices with sharp red emission,Jpn. J. Appl. Phys., Part 1, 34(4A)(1995):1883～1887.
[47] J. Kido, H.Haromichi, K.Hongawa,etc.,Bright and light-emitting Oganic electroluminescent devices having an europium complexes as all emitter, Appl. Phys.Lett., 65(17)(1994): 2124.
[48] O.kada, Wang, Yanfeng;etc. Bright red light-emitting organic electroluminecent devices based on a novel thiophene-containing europium complex as an emitting layer. J. Mater. Chem., 9(12)(1999): 3023～3026.
[49] J.Kido,I.Wataru,K.Masato, etc., White-light-emitting organic EL device using lanthanide complexes, Jpn. J. Appl. Phys.,Part 2, 35(3B)(1996): L394.
[50] R.J.Curry, W.P.Gillin, Infra-red and visible EL from Erq3 based OLEDs, Synth.Met. 111～112(2000):35～38.
[51] Hong, I.,Li ,W.L.,Zhao,D.,etc.,White light emiision from OEL devices based on organic dysprosium complex, Synth. Met. 111～112(2000):43～45.
[52] Zhao,D., Hong,Z., Liang,C.,etc., Enhanced EL of europoium(III) complex by terbium(III) substitution in org. emitting diodes, Thin Solid Films,363(12)(2000):208～210.
[53] W. G. Zhu, Q. Jiang, Z.Y. Lu, X. Q. Wei, M. G. Xie, D. C. Zou, T. Tsutsui, Novel binuclear europiumβ-diketone chelate used as red emitter in org EL device, The Solid Films, 363(2000): 167～169.
[54] Zhu,W.G.,etc.,Synthesis and fluorescent properties of new binuclear europium β-diketone chelate EumY1-m(TTA)3phen as red EL materials,Chin Chem.Lett.,10(7)(1999):603～606.
[55] 高改玲，张安运，钱博等，化学通报，6（1997），42～44.
[56] Yong Qiu, Yan Shao, Deqiang Zhang, et al,Preparation and Characterization of High Efficient Blue-LightEmitting Materials with a secondary, Jpn.ligands for organic Electroluminescence J. Appl. Phys., Part 1 39(3A)(2000):1151～1153.
[57] 李文连，稀土有机电致发光研究进展，中国稀土学报， 17（3）（1999）：267～270。
[58] 阎冰，张洪杰，王淑彬等，稀土N-苯基邻氨基苯甲酸-1，10-邻菲罗啉二元、三元配合物的合成、表征及光物理性质，高等学校化学学报，19（5）（1998）：671～675。
[59] 徐志栋，王敏等，稀土发光配合物的研究，应用化学， 2（1999）：18。
[60] 王敏，徐志栋等，稀土元素与环己基甲酸邻菲罗啉三元固态配合物的合成和性质的研究，无机化学学报，13（3）（1997）：347。
[61] 李建平，王宝兰等，部分稀土与邻苯二甲酸及邻菲罗啉三元配合物的荧光性质，湖北大学学报（自然科学版）， 18（4）（1996）：379。
[62] 王流芳，任艳平等，混合配体、稀土三元配合物的研究，无机化学学报，，9（2）（1993）：123。
[63] 孙波，赵莹等，光谱学与光谱分析，17（2）（1997）：25～29。
[64] 李斌、张洪杰等，双亲性稀土-邻苯二甲酸正十四醇单酯-邻菲罗啉三元配合物的合成、表征、荧光特性及成膜性能，无机化学学报，14（2）（1998）：233。
[65] 孙刚， 李文连，发光学报，17（1997）：93。
[66] 孙刚， 李文连，发光学报，17（1997）：89。
[67] Abiaziz A. Farah, William J. Pietro,Synthesis and Charcterization of partially crosslinked poly(N-vinylcarbazole- vinylalcohol) copolymer with polypyridyl Ru(Ⅲ) luminophores: Potential materials for electroluminescence, Polymer Buelletin, 43(2～3)（1999）: 135～142.
[68] 曾云鹗，张华山，陈震华编，现代化学试剂手册，第4分册，无机离子显色剂，化学工业出版社（第一版），北京，（1989）：575～576。
[69] 姜麟忠编，催化氢化在有机合成中的应用，化学工业出版社（第一版），北京，（1987）,７７～７８。
[70]Emil Koft and Francis H. Case, Substituted 1,10-Phenanthrolines，XII. Beno and Pyride Derivatives. J.Org. Chem., 27(3)(1962): 865～868.
[71]段长强，孟庆芳，张泰等编，现代化学试剂手册，第一分册，通用试剂，化学工业出版社（第一版），北京，（1988）：544。
[72] Kerry. P. McNamara, Xuepeng, Li, Angela D. Stull, Zeev Rosenzweig, Fiber-optic oxygen sensor based on the fluorescence quenching of tis(5-acrylamido-phenanthroline) ruthenium chloride, Analytic Chimice Acta 361(1998), 73～83.
[73] B.S.Jensen, Acta Chem.Scond.,13(1959)61:1668.
[74] G.F. Smith and F. W Cagle, The Improvemed Synthesis of 5-Nitro-1,10-Phenanthroline, J. Org. Chem., 12(1947):781～784.
[75] 陈国真，黄贤智，郑朱梓等编著，荧光分析法，科学出版社（第二版），北京,（1990），43～44。
[2] D.D.C.Bradley, Synth. Met., 54(1993): 401.
[3] C.W.Tang,S.A.V.Slyke,Appl.Phys.Lett.,51(1987):913.
[4]C.Adachi,S.Tokito,T.Tsutsui et al.,Jpn.J.Appl.Phys.,27 (1988):L7113.
[5] J.H.Burroughes, D.D. C. Bradley, A. R. Brown, R.N.Marks, K. Mackey, R.H. Friend, P. L. Burn, A.B. Holmes.,Nature, 347(1990):539.
[6]J.L.Segura.,The chemistry of electroluminescent organic materials, Acta Polym.,49(1998): 319～344.
[7] 李文连，有机EL进展，液晶与显示，11（3）(1996)：218～226。
[8] Y. Hamade, IEEE Transaction on electron Devices, 44(8) (1997)：1208.
[9] S.A.V.Slyke,C.H.Chen,C.W.Tang,Organic Electrluminecent devices with improved stability, Appl. Phys. Lett., 69(15)(1996):2160～2162.
[10] N. Masakatsu, K.Noriko, JP 11-54283(99 054 283).
[11] I.Koan, Jpn. Kokai Tokkyo Kohn, JP 07-26254(95 026 254 ).
[12] 张晓宏，吴世康等，几种吡唑啉酮衍生物的光致发光和电致发光特性研究，化学学报，58（3）（2000）：293～296。
[13] C. P. Lin, et al. Jpn.Polym.Res., 2(3) （1995）: 133～138.
[14] 赵云祥， 闻天泽，分析化学中的配位化合物， 北京大学出版社， (1986):275～281。
[15] T. Nakocyama, T.Tsutsui, Enhancement in I-D optical resonator devices with organic films ,Synth. Met., 91（1997）: 58.
[16] 朱卫国，苑同锁， 卢志云，谢明贵，材料导报，1(2000):50～54
[17] J.Kido, et al, Chem. Lett. (1991): 267
[18] Y. Hamada, T. Sano, M. Fujita, etc.Organic Electroluminecent Devices with 8-hydroxyquinoline Derivative-Metal Complexes as an Emitter, Jpn.J. Appl. Phys., 32(4A)（1993）: L514～515.
[19] A.Fujii, M.Yoshida,et al, Color-variable Electrluminescent diode with Single quantum Well Structure Utilizing 8-hydroxqinoline
[20] J. Kido, K. Nagai, Y. Okamoto,etc. Chem. Lett., (1991):1267.
[21] M. Granstr?m and O. Ingan?s, White light emission from a polymer blend light emitting diode,Appl. Phys. Lett.,68(2)( 1996):147～149.
[22]K.Okada,M.Uekawa,Y.F.Wang,etc.,T.Nakaya,Chem.Lett.,(1998):80.
[23] M. Vekawa, Y. Miyamoto, H. Ikeda, Kaifu, T. Nakaya, Bull. Chem. Soc. Jpn.,71(1998): 2253～2258.
[24] Y. Hamada, T. Sano, M. Fujita,etc.,Blue Electroluminecence in Thin Film of Azomethin-Zinc Complexes, Jpn. J. Appl. Phys. 32(4A) (1993):L511.
[25] J. Kido, K. Okuyama, K. Nagai,White light-emitting orgnic electrolumineslentt devices using the poly(N-vinylcarbazole) emitter layer doped with three fluorescent dyes,Appl. Phys. Lett., 64(7) (1994):815～817.
[26] Y. Hamada, T. Sano, M. Fujita, T. Fujii, Y. Nishio and K. Shitata, White-light Emitting Material for organic eledtroluminescentt Devices,Jpn. J. Appl. Phys. 35(10B)(1996):L1339～L1341
[27] J. Kido, Y. Lizumi,Fabrication of highly efficinent organic electrouminescent devices,Appl. Phys. Let., 73(19) (1998): 2721～2723.
[28] J.Kido, K.Hongawa, K.Okuyama, K.Nagai, Bright blue electro- luminescente from poly(N-vinylcarbazole), Appl. Phys. Lett.63 (19) (1993):2627.
[29]I.Sokolik, Z.Yang, F.E.Karasz, D.C.Morton, Blue-light electro- luminescente from p-phenylene vinelene-based copolymers Appl. Phys., 74(1993):3584.
[30] Y.Ohamai M.Uchida,K.Nuro,K.Koshino,Solid State Com.,80(1991): 605.
[31] N. C.Greenham, S.C. Moraft, D.D.C.Bradley et al. Nature, 365(1993):628.
[32] G.Emmanuette, J.Michel, C.Sentein, et al. Synth. Metals, 81(1996):197.
[33] J. Bharathan and Y. Yang , Polymer electroluminescent devices processed by inject printing:I.Polymer Light-emitting Logo ,Appl. Phys. Lett., 72(1998): 2660.
[34]Hong Meng, Wang-Lin Yu, Wei Huang, Facil Synthetic Route to a Novel Electroluminescent Polymer Poly(p-phenylenevinylene) Containing a Fully Conjugated Aromatic Oxdiazole Side Chain, Macromolecules, 32(1999):8841.
[36] Ching-Lan Chao, Show- An Chen, White light emission from exciplex in a bilayer device with two blue light-emmitting polymers, Appl. Phys.Lett.73(4)( 1998): 426～428.
[37]Xue Zhang, A.S., Shetty, S.A. Jenekhe, Electroluminescence and Ptotophysical Properties of Polyquinolines, Macromolecules, 32(1999): 7422
[38] T. Ohnisti, S. Doi, Y. Tsuchida, T. Noguchi, IEEE Transaction on Electron Devices, 44(8)( 1997): 1253～1257.
[39] 曹红，高希存，黄春辉等，比唑啉衍生物作为空穴传输层在电致发光材料中的应用，感光科学与光化学，17（4）（1999）：357～359。
[40]Kathirgamanathan, Poopathy. Electroluminescent materials. WO 00 26,323.
[41]Yamaguchi, Takahito; Ota, Masabumi, etc. Org.EL.element. JP 05,17,766[93,17,766].
[42]Hu,Mai-Liu; Huang,Zhenyan; Cheng,Yaqian, etc.Crystal Structure and fluorescence spectrum of the complex Eu(TTA)3phen, Chin. J. Chem. 17(6)(1999):637～643.
[43] 李文连，有机电致发光发射材料用金属络合物研究，功能材料，28(2)(1997)：109～114。
[44] Michacl D.,McGehee,Bergstedt,Troy,etc.,Narrow bandwith luminescence from blends with energy transfer from semiconducting conjugated polymers to europium complexes., Adv. Mater. 11(16)(1999): 1349～1354.
[45]Noriyuki Takada, Tetsuo,Tsutsui and Shogo Saito., Strongly Directed Emission from Controlled-Spontaneous-Emission EL Diodes with Europium Comolex as an Emitter. Jpn.J.Appl.Phys.,Part 2,33(6B)(1994),L863～866.
[46]S., Takeski; Fujita, Masayuki,etc.,Novel europium complex for EL devices with sharp red emission,Jpn. J. Appl. Phys., Part 1, 34(4A)(1995):1883～1887.
[47] J. Kido, H.Haromichi, K.Hongawa,etc.,Bright and light-emitting Oganic electroluminescent devices having an europium complexes as all emitter, Appl. Phys.Lett., 65(17)(1994): 2124.
[49] J.Kido,I.Wataru,K.Masato, etc., White-light-emitting organic EL device using lanthanide complexes, Jpn. J. Appl. Phys.,Part 2, 35(3B)(1996): L394.
[50] R.J.Curry, W.P.Gillin, Infra-red and visible EL from Erq3 based OLEDs, Synth.Met. 111～112(2000):35～38.
[51] Hong, I.,Li ,W.L.,Zhao,D.,etc.,White light emiision from OEL devices based on organic dysprosium complex, Synth. Met. 111～112(2000):43～45.
[52] Zhao,D., Hong,Z., Liang,C.,etc., Enhanced EL of europoium(III) complex by terbium(III) substitution in org. emitting diodes, Thin Solid Films,363(12)(2000):208～210.
[53] W. G. Zhu, Q. Jiang, Z.Y. Lu, X. Q. Wei, M. G. Xie, D. C. Zou, T. Tsutsui, Novel binuclear europiumβ-diketone chelate used as red emitter in org EL device, The Solid Films, 363(2000): 167～169.
[54] Zhu,W.G.,etc.,Synthesis and fluorescent properties of new binuclear europium β-diketone chelate EumY1-m(TTA)3phen as red EL materials,Chin Chem.Lett.,10(7)(1999):603～606.
[55] 高改玲，张安运，钱博等，化学通报，6（1997），42～44.
[56] Yong Qiu, Yan Shao, Deqiang Zhang, et al,Preparation and Characterization of High Efficient Blue-LightEmitting Materials with a secondary, Jpn.ligands for organic Electroluminescence J. Appl. Phys., Part 1 39(3A)(2000):1151～1153.
[57] 李文连，稀土有机电致发光研究进展，中国稀土学报， 17（3）（1999）：267～270。
[58] 阎冰，张洪杰，王淑彬等，稀土N-苯基邻氨基苯甲酸-1，10-邻菲罗啉二元、三元配合物的合成、表征及光物理性质，高等学校化学学报，19（5）（1998）：671～675。
[59] 徐志栋，王敏等，稀土发光配合物的研究，应用化学， 2（1999）：18。
[60] 王敏，徐志栋等，稀土元素与环己基甲酸邻菲罗啉三元固态配合物的合成和性质的研究，无机化学学报，13（3）（1997）：347。
[62] 王流芳，任艳平等，混合配体、稀土三元配合物的研究，无机化学学报，，9（2）（1993）：123。
[63] 孙波，赵莹等，光谱学与光谱分析，17（2）（1997）：25～29。
[64] 李斌、张洪杰等，双亲性稀土-邻苯二甲酸正十四醇单酯-邻菲罗啉三元配合物的合成、表征、荧光特性及成膜性能，无机化学学报，14（2）（1998）：233。
[65] 孙刚， 李文连，发光学报，17（1997）：93。
[66] 孙刚， 李文连，发光学报，17（1997）：89。
[67] Abiaziz A. Farah, William J. Pietro,Synthesis and Charcterization of partially crosslinked poly(N-vinylcarbazole- vinylalcohol) copolymer with polypyridyl Ru(Ⅲ) luminophores: Potential materials for electroluminescence, Polymer Buelletin, 43(2～3)（1999）: 135～142.
[68] 曾云鹗，张华山，陈震华编，现代化学试剂手册，第4分册，无机离子显色剂，化学工业出版社（第一版），北京，（1989）：575～576。
[69] 姜麟忠编，催化氢化在有机合成中的应用，化学工业出版社（第一版），北京，（1987）,７７～７８。
[70]Emil Koft and Francis H. Case, Substituted 1,10-Phenanthrolines，XII. Beno and Pyride Derivatives. J.Org. Chem., 27(3)(1962): 865～868.
[71]段长强，孟庆芳，张泰等编，现代化学试剂手册，第一分册，通用试剂，化学工业出版社（第一版），北京，（1988）：544。
[72] Kerry. P. McNamara, Xuepeng, Li, Angela D. Stull, Zeev Rosenzweig, Fiber-optic oxygen sensor based on the fluorescence quenching of tis(5-acrylamido-phenanthroline) ruthenium chloride, Analytic Chimice Acta 361(1998), 73～83.
[73] B.S.Jensen, Acta Chem.Scond.,13(1959)61:1668.
[74] G.F. Smith and F. W Cagle, The Improvemed Synthesis of 5-Nitro-1,10-Phenanthroline, J. Org. Chem., 12(1947):781～784.
[75] 陈国真，黄贤智，郑朱梓等编著，荧光分析法，科学出版社（第二版），