新型有机电致发光材料的制备及其性能研究
摘要
用于OLED(Organic Light Emitting Diodes)的磷光材料主要包括一些重金属如铱、铂等的配合物,这些配合物中心离子d轨道上强烈的自旋轨道耦合导致单重态和三线态能级的混合而出现三线态发光,从而使得材料的内量子效率可由25%提升至近100%。其中金属铱配合物因具有短的磷光寿命和高的发光效率而成为研究的热点。通过对配体的设计和改造,可以改变发光材料的性能、改善主客体材料的相容性,从而提高器件的发光效率、亮度,延长器件的使用寿命。本论文针对目前磷光材料和器件存在的问题,例如：三线态激子寿命过长,发光效率,品质不高等等,进行了新型环金属铱配合物的分子设计、合成及其电致发光性能的研究。
本论文工作主要设计过程包括两个方面,一是合成一系列新型的配体,将这些配体与三氯化铱反应,得到新的环金属铱的配合物,对这些配合物用核磁荧光光谱以及紫外光谱等进行结构表征；二是用合成的配合物作为发光客体,掺杂于发光主体4,4'-N,N'-dicarbazole-biphenyl (CBP)中,制备多层结构的电致发光器件,研究它们的电致发光性质。具体的工作主要包括：
1、对传统的2-芳基吡啶类的配体进行结构修饰,合成了四个具有不同共轭体系的金属配体,期望在吡啶环的4-位接入不同的取代基如苯基,甲基,叔丁基等,从而调节配体的共轭体系,以获得满意的能量传输效率,发光波长,并且能够产生一定的空间效应,减少三重态激子的自淬灭现象；在苯环上进行氟代,改善发光性能,利于蒸镀,增加成膜性并提高器件的稳定性,通过这些配体和三氯化铱反应合成十二个新的配合物,利用1HNMR、13CNMR、PL、以及UV等对配合物进行结构表征。以配合物Ir(DFPP)2(pic)作为发光客体掺杂于主体材料CBP中,制备工多层结构的器件,在6伏左右的低驱动电压下,器件能发射比较强的蓝绿色磷光,波长为498nm,最高亮度为24220 cd/m2,最大效率为5.47 cd/A,量子效率为3.05%。结果表明,器件呈现电致磷光发光特性,器件的发光波长与配体结构有关系,在C^N配体接入取代基氟后,发射波长会产生蓝移；增加配体的共轭体系,发射波长产生红移。
2、设计、合成了两个新型的具有一定刚性或较小可扭转度、不同共轭程度的环金属配体,并以此制备了四个相应的铱配合物,利用1HNMR、13CNMR、PL、以及UV等对配合物进行结构表征。以配合物(BIIO)2Ir(acac)作为发光客体掺杂于主体材料CBP中,研究了它们的电致发光性质。在6袄的低压驱动下,器件的发光波长为498 nm,其最大亮度和最大外量子效率,分别为79640 cd/m2和11.2%。结果表明此类刚性配体可以提高配合物的外量子效率,亮度并且对光色有较好的改变。
The heavy metals such as Ir, and Pt complexes have been widely employed as luminescent materials in OLED (Organic Light Emitting Diodes). Owing to the strong spin-orbital mixing of heavy-metal ions in phosphorescent complexes, both singlet and triplet excitons can be fully utilized, which creates the possibility for reaching a maximum internal efficiency of 100%. In these materials, iridium complexes have been regarded as one of the most appropriate phosphorescent materials because of their relative short lifetime and high quantum efficiency. The properties of these devices, such as efficiency, brightness, and life are strongly depended on structure of the cyclometalated ligands. Cyclometalated iridium complexes using as electrophosphorescent materials were studied and are partly resolved present problems of electrophosphorescent materials and devices.
Our studies are focused on the synthesis, characterization of new cyclometalated iridium complexes and electroluminescent properties in multilayer devices. The contexes are followed in this dissertation:
1. Synthesis, characterization and luminescence study of iridium complexes with 2-arylpyridine and its derivates as cyclometalated ligands.
A series of new cyclometalated ligands with different conjugation system and different substituents have been synthesized by changing 2-phenylpyridine. It is certainly possible to change the wavelength of emission of the complex by modifying the phenylpyridine ligand. Additional efforts show that it is possible to reduce self-quenching by the introduction of bulky groups on the basic phenylpyridine ligand. And also, fluorinated substituents on the aromatic ligand can result in markedly reduced concentration-quenching of luminescence, and excellent volatility which aids device processing. Reaction of these cyclometalated ligands with IrCl3·3H2O afforded the iridium complexes by changing different ancillary ligands. The obtained complexes have been characterized by 1H NMR, PL, and UV. The devices fabricated using the complexe Ir(DFPP)2(pic) as a dopant emitter has been achieved in a multilayer configuration. The maximum brightness of the device based on Ir(DFPP)2(pic) is 24220 cd/m2 with an external quantum efficiency of 3.05%. Its maximum efficiency is 5.47 cd/A
2. Synthesis, characterization and luminescence study of iridium complexes with rigid cylcometalated ligands
A series.of new Iridiunm complexes with rigid cylcometalated ligands have been synthesized. The obtained complexes have been characterized by 1H NMR, PL and UV. The complex Ir(BIIO)2(pic) was used as an emitter in a multilayer configuration devices. The results showed that these complexes have strong phosphorescent characters. The device with a maximum external quantum efficiency of 11.2% and a maximum brightness of 79640 cd/m2 were achieved.
本论文工作主要设计过程包括两个方面,一是合成一系列新型的配体,将这些配体与三氯化铱反应,得到新的环金属铱的配合物,对这些配合物用核磁荧光光谱以及紫外光谱等进行结构表征；二是用合成的配合物作为发光客体,掺杂于发光主体4,4'-N,N'-dicarbazole-biphenyl (CBP)中,制备多层结构的电致发光器件,研究它们的电致发光性质。具体的工作主要包括：
1、对传统的2-芳基吡啶类的配体进行结构修饰,合成了四个具有不同共轭体系的金属配体,期望在吡啶环的4-位接入不同的取代基如苯基,甲基,叔丁基等,从而调节配体的共轭体系,以获得满意的能量传输效率,发光波长,并且能够产生一定的空间效应,减少三重态激子的自淬灭现象；在苯环上进行氟代,改善发光性能,利于蒸镀,增加成膜性并提高器件的稳定性,通过这些配体和三氯化铱反应合成十二个新的配合物,利用1HNMR、13CNMR、PL、以及UV等对配合物进行结构表征。以配合物Ir(DFPP)2(pic)作为发光客体掺杂于主体材料CBP中,制备工多层结构的器件,在6伏左右的低驱动电压下,器件能发射比较强的蓝绿色磷光,波长为498nm,最高亮度为24220 cd/m2,最大效率为5.47 cd/A,量子效率为3.05%。结果表明,器件呈现电致磷光发光特性,器件的发光波长与配体结构有关系,在C^N配体接入取代基氟后,发射波长会产生蓝移；增加配体的共轭体系,发射波长产生红移。
2、设计、合成了两个新型的具有一定刚性或较小可扭转度、不同共轭程度的环金属配体,并以此制备了四个相应的铱配合物,利用1HNMR、13CNMR、PL、以及UV等对配合物进行结构表征。以配合物(BIIO)2Ir(acac)作为发光客体掺杂于主体材料CBP中,研究了它们的电致发光性质。在6袄的低压驱动下,器件的发光波长为498 nm,其最大亮度和最大外量子效率,分别为79640 cd/m2和11.2%。结果表明此类刚性配体可以提高配合物的外量子效率,亮度并且对光色有较好的改变。
The heavy metals such as Ir, and Pt complexes have been widely employed as luminescent materials in OLED (Organic Light Emitting Diodes). Owing to the strong spin-orbital mixing of heavy-metal ions in phosphorescent complexes, both singlet and triplet excitons can be fully utilized, which creates the possibility for reaching a maximum internal efficiency of 100%. In these materials, iridium complexes have been regarded as one of the most appropriate phosphorescent materials because of their relative short lifetime and high quantum efficiency. The properties of these devices, such as efficiency, brightness, and life are strongly depended on structure of the cyclometalated ligands. Cyclometalated iridium complexes using as electrophosphorescent materials were studied and are partly resolved present problems of electrophosphorescent materials and devices.
Our studies are focused on the synthesis, characterization of new cyclometalated iridium complexes and electroluminescent properties in multilayer devices. The contexes are followed in this dissertation:
1. Synthesis, characterization and luminescence study of iridium complexes with 2-arylpyridine and its derivates as cyclometalated ligands.
A series of new cyclometalated ligands with different conjugation system and different substituents have been synthesized by changing 2-phenylpyridine. It is certainly possible to change the wavelength of emission of the complex by modifying the phenylpyridine ligand. Additional efforts show that it is possible to reduce self-quenching by the introduction of bulky groups on the basic phenylpyridine ligand. And also, fluorinated substituents on the aromatic ligand can result in markedly reduced concentration-quenching of luminescence, and excellent volatility which aids device processing. Reaction of these cyclometalated ligands with IrCl3·3H2O afforded the iridium complexes by changing different ancillary ligands. The obtained complexes have been characterized by 1H NMR, PL, and UV. The devices fabricated using the complexe Ir(DFPP)2(pic) as a dopant emitter has been achieved in a multilayer configuration. The maximum brightness of the device based on Ir(DFPP)2(pic) is 24220 cd/m2 with an external quantum efficiency of 3.05%. Its maximum efficiency is 5.47 cd/A
2. Synthesis, characterization and luminescence study of iridium complexes with rigid cylcometalated ligands
A series.of new Iridiunm complexes with rigid cylcometalated ligands have been synthesized. The obtained complexes have been characterized by 1H NMR, PL and UV. The complex Ir(BIIO)2(pic) was used as an emitter in a multilayer configuration devices. The results showed that these complexes have strong phosphorescent characters. The device with a maximum external quantum efficiency of 11.2% and a maximum brightness of 79640 cd/m2 were achieved.
引文
[1]M. Pope, H. P. Kallmann, P. Magnate. J. Chem. Phys.,38(1963),2042
[2]W. Helfrich, W. G. Schneider. Phys. Rev. Lett.,14(1965),229
[3]D. F. Williams, M. Schadt. Pro. IEEE.,58(1970),476
[4]P. S. Vincett, W. A. Barlow, R. A. Hann, G. G. Roberts. Thin Solid Film,94(1982), 171
[5]C. W. Tang, S. A. VanSlyke. Appl. Phys. Lett, 51(1987),913
[6]J. H. Burroughs, D. D. C. Bradley, A. R. Brown, R. N. Marks, et al. Nature, 347(1990),539
[7]Y. G. Ma, H. Y. Zhang, J. C. Shen., C. M Che. Synth. Met.,94(1998),245
[8]M. A. Baldo, D. F. O'Brien, M. E. Thompson, S. R. Forrest, et al. Nature, 395(1998),151
[9]Y. Fududa, T. Watanabe, T. Wakimoto, S. Miyaguchi, et al. Syth. Met.,111(2000), 1
[10]黄春辉,李富友,黄岩谊,光电功能超薄膜，北京大学出版社,(2001),244
[11]孙毓庆,胡育筑,李章万,分析化学，科学出版社,(2003),275
[12]P. M. Borsenberger, W. Mey, A. Chowdry. Appl. Phys.,49(1978),293
[13]K. Yamashita, T. Mori, T. Mizutani, H. Miyazaki, T. Takeda. Thin Solid Films, 363(2000),33
[14]M. Kimura, S. Inoue, K. Shimada, S. Tokito, et al. Chem. Lett., (2000),192
[15]I. Y. Wu, J. T. Lin, Y. T.Tao, E. Balasubramaniam. Adv. Mater.,12(2000),668
[16]T. Sano, Y. Nishio, Y. Hamada, H. Takahashi, et al. J. Org. Chem.,10(2000),157
[17]M. A. Baldo, M. E. Thompson, S. R. Forrest. Pure Appl. Chem.,71(1999),2095
[18]X. Gong, M. R. Robinson, J.C. Ostrowski, D. Moses, et al. Adv. Mater., 14(2002),581
[19]X. Gong, J. C. Ostrowski, D. Moses, G. C. Bazan, et al. Adv. Funct. Mater., 13(2003),439
[20]C. Jiang, W. Yang, J. Peng, S. Xiao, Y. Cao, Adv. Mater.,16(2004),537
[21]T. Tsutsui, M. J. Yang, M. Yahiro, et al. J. Appl. Phys.38(1999),1502
[22]S. C. Lo, A. H. Male, J. P. J. Markam, et al. Adv. Mater.14(2002),975
[23]X. Gong, J. C. Ostrowski, G. C. Bazan, et al. Appl. Phys. Lett.,81(2002),3711
[24]S. Lamansky, P. Djurovich, D. Murphy, et al. J. Am. Chem. Soc.,123(2001), 4304
[25]S. Lamansky, P. Djurovich, M. E.Thompson, et al. Inorg. Chem.,40(2001), 1704
[26]Y. J. Su, H. L. Huang, C. L. Li, R. S. Liu, et al. Adv. Mater.,15(2003),884
[27]J. P. Duan, P. P. Sun, C. H. Cheng, et al. Adv. Mater.,15(2003),224
[28]B. M. J. S. Paulose, D. K. Rayabarapu, C. H. Cheng. Adv. Mater.,16(2004), 2003
[29]H. C. Li, P. T. Chou, Y. H. Hu, et al. Organometallics 24(2005),1329
[30]S. Lamansky, R. C. Kwong, M. Nugeny, et al. Org. Electronics 2(2001),53
[31]P. I. Djurovich, A. Tamayo, M. E. Thompson, et al. Abs. 3nd Internat. Conf.(ICEL-3), p.45, Sept, 5-8,2001, Los Angelos, CA, USA.
[32]S. J. Yeh, M. F. Wu, C. T. Chen, et al. Adv. Mater.,17(2005),285
[33]Lianqing Chen, Han You, Chuluo Yang. Dongge Ma, et al. Chemcomm, (2007), 1352-1354
[1]M. A. Baldo, D. F. O'Brien, M. E. Thompson, S. R. Forrest, et al. Nature, 395(1998),151
[2]Y. Ma, H. Zhang, J. Shen, et al. Synth. Met.,94(1998),245
[3]Y. Ma, C. M. Che, H. Y. Chao, et al. Adv. Mater.,11(1999),852
[4]C. K. Hugo, M. Y. Ngai, S. C. Chan, et al. Inorg. Chem.,44(2005),4442
[5]Y. L. Tung, P. C. Wu, C. S.Liu, et al. Organometallic, 23(2004), 3745
[6]L. Huang, K. Z. Wang, C. H. Huang, et al. J. Mater. Chem.,11(2006),790
[7]J. K. Lee, D. S. Yoo, E. S. Handy, et al. Appl. Phys. Lett.,69(1996),1686
[8]C. Adachi, M. A. Baldo, S. Lamansky, et al. Appl. Phys. Lett.,77(2000),904
[9]M. Ikai, S. Tokito, Y. Sakamoto, T. Suzuki, et al. Appl. Phys. Lett.,79(2001),156
[10]C. Adachi, M. A. Baldo, M. E. Thompson, et al. J. Appl. Phys.,90(2001),4988
[11]R. C. Kwong, M. R. Nugent, L. Michalski, et al. Appl. Phys. Lett., 81(2002), 162
[12]M. A. Baldo, S. Lamansky, M. E. Thompson, et al. Appl. Phys. Lett.,75(1999), 4
[13]V. V. Grushin, N. Herron, D. D. LeClour, et al. Chem. Commun., (2001),1494
[14]S. Lamansky, P. Djurovich, D. Murphy, J. Am. Chem. Soc.,123(2001),4304
[15]W. G. Zhu, Y. Q. Mo, M. Yuan, et al. Appl. Phys. Lett.,80(2005) 2045
[16]Y. Yang, N. Herron, V. V. Grushin, et al. Appl. Phys. Lett.,79(2006),449
[17]F. Krohnke, Synthesis, (1976),1-24
[18]C. C. Cheng, W. S. Yu, P. K. Zhou, et al. Chem. Commun.,2003,2628
[19]P. C. Wu, J. K. Yu, Y H. Song, et al. Organometallitics, 22(2003),4938
[20]J. Kavitha, S. Y. Chang, Y. Chi, et al. Adv. Funct. Mater.,15(2005),223
[21]M. Nonoyama, Bull. Chem. Soc. Jpn.,47(1974),767
[22]J. Brooks, Y. Babayan, S. Lamansky, et al. Inorg. Chem.,41(2002), 3055
[23]S. Lamansky, P. Djurovich, D. Murphy, et al. Inorg. Chem.,40(2001),1704
[24]J. Ding, J. Gao, Q. Fu, et al. Synth. Met.,155(2005),539
[25]K. R. Justin Thomas, M. Velusamy, J. T. Lin, et al. Inorg. Chem.,44(2005), 5677
[26]J. Li, P. I. Djurovish, B. D. Alleyne, et al. Inorg. Chem.,44(2005),1713
[27]W. S. Huang, J. T. Lin, C. H. Chien, et al. Chem. Mater.,16(2004),2480
[28]P. J. Hay, J. Phys. Chem. A.,106(2002),1634
[29]M. G. Colomobo, T. C. Brunold, T. Riedener, et al. Inorg. Chem.,33(1994),545
[30]A. Tsuboyama, H. Iwawaki, M. Furugori, et al. J. Am. Chem. Soc.,125(2006), 12971
[1]M. A. Baldo, D. F. O'Brien, Y. You, S. R. Forrest, et al. Nature,395(1998),151
[2]S. Lamansky, P. Djurovich, D. Murphy, et al. J. Am. Chem. Soc.,123(2001), 4304
[3]S. Lamansky, P. Djurovich, M. E.Thompson, et at. Inorg. Chem.,40(2001),1704
[4]A. B. Tamayo, B. D. Alleyne, M. E. Thompson, et al. J. Am. Chem. Soc., 125(2003),7377
[5]J. Q. Ding, J. Gao, Q. Fu, L. X. Wang, et al. Synth. Met.,155(2005),539
[6]K. R. J. Thomas, M. Velusamy, J. T. Lin, Y. T. Tao, et al. Inorg. Chem.,44(2005), 5677
[7]H. C. Li, P. T. Chou, Y. H. Hu, R. S. Liu, et al, Organometallics, 24(2005), 1329
[8]W. S. Huang, J. T. Lin, C. H. Chien, Y. T. Tao, et al. Chem. Mater.,16(2004), 2480
[9]黄春辉,李富友,黄维,复旦大学出版社,有机电致发光材料与器件导论,(2005),24
[10]孙毓庆,胡育筑,李章万,科学出版社,分析化学，(2003),,275
[11]J. P. Duan, P. P. Sun, C. H. Cheng, et al. Adv. Mater.,15(2003),224
[12]L.C. Rong, J.X. Wang, Q.Y. Zhuang, D.Q. Shi, Xuzhou Shifan Daxue Xuebao, Ziran Kexueban 21(2003) 33.
[13]A. H. Jackson, P. V. R. Shannon, P. W. Taylor, J. Chem. Soc. Perkin Ⅱ, (1982), 289
[14]吴利欢,杨定乔,吕芬,杨世柱,化学试剂，26(2004),103
[15]A. H. Jackson, P. V. R. Shannon, P. W. Taylor, J. Chem. Soc. Perkin Ⅱ, (1981), 286
[16]E. L. Martin, J. Am. Chem. Soc.,58(1936),1438
[17]K. Satish; K. S. Sharma, Indian J. Chem. Section B:20B (1981),380
[18]徐宝峰,赵爱华,化学世界43(2002),374
[19]L. F. Fieser, M. D. Gates, J. Am. Chem. Soc.,62(1940),2335
[20]Bliche, Burckhalter, J. Am. Chem. Soc.,64(1942),453
[21]F. Andreani, R. Andrisano, G. Salvadori, et al. J. Chem. Soc.(C), (1971),1007
[22]J. Ding, J. Gao, Q. Fu, et al. Synth. Met.,155(2005),539
[23]J. Li, P. I. Djurovish, B. D. Alleyne, et al. Inorg. Chem.,44(2005),1713
[24]W. S. Huang, J. T. Lin, C. H. Chien, et al. Chem. Mater.,16(2004),480
[25]H. C. Li, P. T.Chou, Y. H. Hu, et al. Organometallics,24(2005),1329
[26]J. Li, P. I. Djurovish, B.D. Alleyne, et al. Inorg. Chem.,44(2005),1713
[27]K. R. J. Thomas, M. Velusamy, J. T. Lin, et al. Inorg. Chem.,44(2005),5677
[28]P. J. Hay, J. Phys. Chem. A,106(2002),1634
[29]M. G Colomobo, T. C. Brunold, T. Riedener, et al. Inorg. Chem.,33(1994),54
[2]W. Helfrich, W. G. Schneider. Phys. Rev. Lett.,14(1965),229
[3]D. F. Williams, M. Schadt. Pro. IEEE.,58(1970),476
[4]P. S. Vincett, W. A. Barlow, R. A. Hann, G. G. Roberts. Thin Solid Film,94(1982), 171
[5]C. W. Tang, S. A. VanSlyke. Appl. Phys. Lett, 51(1987),913
[6]J. H. Burroughs, D. D. C. Bradley, A. R. Brown, R. N. Marks, et al. Nature, 347(1990),539
[7]Y. G. Ma, H. Y. Zhang, J. C. Shen., C. M Che. Synth. Met.,94(1998),245
[8]M. A. Baldo, D. F. O'Brien, M. E. Thompson, S. R. Forrest, et al. Nature, 395(1998),151
[9]Y. Fududa, T. Watanabe, T. Wakimoto, S. Miyaguchi, et al. Syth. Met.,111(2000), 1
[10]黄春辉,李富友,黄岩谊,光电功能超薄膜，北京大学出版社,(2001),244
[11]孙毓庆,胡育筑,李章万,分析化学，科学出版社,(2003),275
[12]P. M. Borsenberger, W. Mey, A. Chowdry. Appl. Phys.,49(1978),293
[13]K. Yamashita, T. Mori, T. Mizutani, H. Miyazaki, T. Takeda. Thin Solid Films, 363(2000),33
[14]M. Kimura, S. Inoue, K. Shimada, S. Tokito, et al. Chem. Lett., (2000),192
[15]I. Y. Wu, J. T. Lin, Y. T.Tao, E. Balasubramaniam. Adv. Mater.,12(2000),668
[16]T. Sano, Y. Nishio, Y. Hamada, H. Takahashi, et al. J. Org. Chem.,10(2000),157
[17]M. A. Baldo, M. E. Thompson, S. R. Forrest. Pure Appl. Chem.,71(1999),2095
[18]X. Gong, M. R. Robinson, J.C. Ostrowski, D. Moses, et al. Adv. Mater., 14(2002),581
[19]X. Gong, J. C. Ostrowski, D. Moses, G. C. Bazan, et al. Adv. Funct. Mater., 13(2003),439
[20]C. Jiang, W. Yang, J. Peng, S. Xiao, Y. Cao, Adv. Mater.,16(2004),537
[21]T. Tsutsui, M. J. Yang, M. Yahiro, et al. J. Appl. Phys.38(1999),1502
[22]S. C. Lo, A. H. Male, J. P. J. Markam, et al. Adv. Mater.14(2002),975
[23]X. Gong, J. C. Ostrowski, G. C. Bazan, et al. Appl. Phys. Lett.,81(2002),3711
[24]S. Lamansky, P. Djurovich, D. Murphy, et al. J. Am. Chem. Soc.,123(2001), 4304
[25]S. Lamansky, P. Djurovich, M. E.Thompson, et al. Inorg. Chem.,40(2001), 1704
[26]Y. J. Su, H. L. Huang, C. L. Li, R. S. Liu, et al. Adv. Mater.,15(2003),884
[27]J. P. Duan, P. P. Sun, C. H. Cheng, et al. Adv. Mater.,15(2003),224
[28]B. M. J. S. Paulose, D. K. Rayabarapu, C. H. Cheng. Adv. Mater.,16(2004), 2003
[29]H. C. Li, P. T. Chou, Y. H. Hu, et al. Organometallics 24(2005),1329
[30]S. Lamansky, R. C. Kwong, M. Nugeny, et al. Org. Electronics 2(2001),53
[31]P. I. Djurovich, A. Tamayo, M. E. Thompson, et al. Abs. 3nd Internat. Conf.(ICEL-3), p.45, Sept, 5-8,2001, Los Angelos, CA, USA.
[32]S. J. Yeh, M. F. Wu, C. T. Chen, et al. Adv. Mater.,17(2005),285
[33]Lianqing Chen, Han You, Chuluo Yang. Dongge Ma, et al. Chemcomm, (2007), 1352-1354
[1]M. A. Baldo, D. F. O'Brien, M. E. Thompson, S. R. Forrest, et al. Nature, 395(1998),151
[2]Y. Ma, H. Zhang, J. Shen, et al. Synth. Met.,94(1998),245
[3]Y. Ma, C. M. Che, H. Y. Chao, et al. Adv. Mater.,11(1999),852
[4]C. K. Hugo, M. Y. Ngai, S. C. Chan, et al. Inorg. Chem.,44(2005),4442
[5]Y. L. Tung, P. C. Wu, C. S.Liu, et al. Organometallic, 23(2004), 3745
[6]L. Huang, K. Z. Wang, C. H. Huang, et al. J. Mater. Chem.,11(2006),790
[7]J. K. Lee, D. S. Yoo, E. S. Handy, et al. Appl. Phys. Lett.,69(1996),1686
[8]C. Adachi, M. A. Baldo, S. Lamansky, et al. Appl. Phys. Lett.,77(2000),904
[9]M. Ikai, S. Tokito, Y. Sakamoto, T. Suzuki, et al. Appl. Phys. Lett.,79(2001),156
[10]C. Adachi, M. A. Baldo, M. E. Thompson, et al. J. Appl. Phys.,90(2001),4988
[11]R. C. Kwong, M. R. Nugent, L. Michalski, et al. Appl. Phys. Lett., 81(2002), 162
[12]M. A. Baldo, S. Lamansky, M. E. Thompson, et al. Appl. Phys. Lett.,75(1999), 4
[13]V. V. Grushin, N. Herron, D. D. LeClour, et al. Chem. Commun., (2001),1494
[14]S. Lamansky, P. Djurovich, D. Murphy, J. Am. Chem. Soc.,123(2001),4304
[15]W. G. Zhu, Y. Q. Mo, M. Yuan, et al. Appl. Phys. Lett.,80(2005) 2045
[16]Y. Yang, N. Herron, V. V. Grushin, et al. Appl. Phys. Lett.,79(2006),449
[17]F. Krohnke, Synthesis, (1976),1-24
[18]C. C. Cheng, W. S. Yu, P. K. Zhou, et al. Chem. Commun.,2003,2628
[19]P. C. Wu, J. K. Yu, Y H. Song, et al. Organometallitics, 22(2003),4938
[20]J. Kavitha, S. Y. Chang, Y. Chi, et al. Adv. Funct. Mater.,15(2005),223
[21]M. Nonoyama, Bull. Chem. Soc. Jpn.,47(1974),767
[22]J. Brooks, Y. Babayan, S. Lamansky, et al. Inorg. Chem.,41(2002), 3055
[23]S. Lamansky, P. Djurovich, D. Murphy, et al. Inorg. Chem.,40(2001),1704
[24]J. Ding, J. Gao, Q. Fu, et al. Synth. Met.,155(2005),539
[25]K. R. Justin Thomas, M. Velusamy, J. T. Lin, et al. Inorg. Chem.,44(2005), 5677
[26]J. Li, P. I. Djurovish, B. D. Alleyne, et al. Inorg. Chem.,44(2005),1713
[27]W. S. Huang, J. T. Lin, C. H. Chien, et al. Chem. Mater.,16(2004),2480
[28]P. J. Hay, J. Phys. Chem. A.,106(2002),1634
[29]M. G. Colomobo, T. C. Brunold, T. Riedener, et al. Inorg. Chem.,33(1994),545
[30]A. Tsuboyama, H. Iwawaki, M. Furugori, et al. J. Am. Chem. Soc.,125(2006), 12971
[1]M. A. Baldo, D. F. O'Brien, Y. You, S. R. Forrest, et al. Nature,395(1998),151
[2]S. Lamansky, P. Djurovich, D. Murphy, et al. J. Am. Chem. Soc.,123(2001), 4304
[3]S. Lamansky, P. Djurovich, M. E.Thompson, et at. Inorg. Chem.,40(2001),1704
[4]A. B. Tamayo, B. D. Alleyne, M. E. Thompson, et al. J. Am. Chem. Soc., 125(2003),7377
[5]J. Q. Ding, J. Gao, Q. Fu, L. X. Wang, et al. Synth. Met.,155(2005),539
[6]K. R. J. Thomas, M. Velusamy, J. T. Lin, Y. T. Tao, et al. Inorg. Chem.,44(2005), 5677
[7]H. C. Li, P. T. Chou, Y. H. Hu, R. S. Liu, et al, Organometallics, 24(2005), 1329
[8]W. S. Huang, J. T. Lin, C. H. Chien, Y. T. Tao, et al. Chem. Mater.,16(2004), 2480
[9]黄春辉,李富友,黄维,复旦大学出版社,有机电致发光材料与器件导论,(2005),24
[10]孙毓庆,胡育筑,李章万,科学出版社,分析化学，(2003),,275
[11]J. P. Duan, P. P. Sun, C. H. Cheng, et al. Adv. Mater.,15(2003),224
[12]L.C. Rong, J.X. Wang, Q.Y. Zhuang, D.Q. Shi, Xuzhou Shifan Daxue Xuebao, Ziran Kexueban 21(2003) 33.
[13]A. H. Jackson, P. V. R. Shannon, P. W. Taylor, J. Chem. Soc. Perkin Ⅱ, (1982), 289
[14]吴利欢,杨定乔,吕芬,杨世柱,化学试剂，26(2004),103
[15]A. H. Jackson, P. V. R. Shannon, P. W. Taylor, J. Chem. Soc. Perkin Ⅱ, (1981), 286
[16]E. L. Martin, J. Am. Chem. Soc.,58(1936),1438
[17]K. Satish; K. S. Sharma, Indian J. Chem. Section B:20B (1981),380
[18]徐宝峰,赵爱华,化学世界43(2002),374
[19]L. F. Fieser, M. D. Gates, J. Am. Chem. Soc.,62(1940),2335
[20]Bliche, Burckhalter, J. Am. Chem. Soc.,64(1942),453
[21]F. Andreani, R. Andrisano, G. Salvadori, et al. J. Chem. Soc.(C), (1971),1007
[22]J. Ding, J. Gao, Q. Fu, et al. Synth. Met.,155(2005),539
[23]J. Li, P. I. Djurovish, B. D. Alleyne, et al. Inorg. Chem.,44(2005),1713
[24]W. S. Huang, J. T. Lin, C. H. Chien, et al. Chem. Mater.,16(2004),480
[25]H. C. Li, P. T.Chou, Y. H. Hu, et al. Organometallics,24(2005),1329
[26]J. Li, P. I. Djurovish, B.D. Alleyne, et al. Inorg. Chem.,44(2005),1713
[27]K. R. J. Thomas, M. Velusamy, J. T. Lin, et al. Inorg. Chem.,44(2005),5677
[28]P. J. Hay, J. Phys. Chem. A,106(2002),1634
[29]M. G Colomobo, T. C. Brunold, T. Riedener, et al. Inorg. Chem.,33(1994),54