新型铕（Ⅲ）配合物的合成、结构及发光性能研究
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摘要
本论文从设计具有优良光致发光(PL)和电致发光(EL)性能的稀土有机配合物发光材料出发，合成了一系列氮杂菲类第二配体和一系列新型酰亚胺类第一配体，在此基础上得到了两个系列的新型铕(Ⅲ)配合物。从结构方面对配合物进行了表征，讨论了配合物的结构与发光性能的关系。用Eu(DBM)_3L(DBM是二苯甲酰甲烷，L是氮杂菲类配体)作为发光材料制备了五个三层EL器件，并对器件的电致发光(EL)性能进行了初步的探讨。
1．合成了五种氮杂菲类第二配体：二吡啶并[2，3-a：2′，3′-c]喹喔啉(dpq)、二吡啶并[2，3-a：2′，3′-c]-7-甲基-喹喔啉(dpmq)、二吡啶并[2，3-a：2′，3′-c]吩嗪(dppz)、二吡啶并[2，3-a：2′，3′-c]-8-甲基-吩嗪(dpmp)和二吡啶并[2，3-a：2′，3′-c]-7，8，9，10-四氢吩嗪(dptp)。用此类配体作第二配体，二苯甲酰甲烷(DBM)和2-噻吩甲酰三氟丙酮(TTA)作第一配体合成了十个铕(Ⅲ)三元配合物。用X-射线衍射发测定了Eu(DBM)_3 dpq、Eu(DBM)_3 dppz和Eu(TTA)_3dpq三种配合物的单晶结构，其中的铕(Ⅲ)离子均表现为八配位的扭曲四方反棱柱构型，配合物分子间都存在较强的π-π相互作用。在紫外光激发下，配合物均表现为较强的铕(Ⅲ)离子特征发射，不同配合物发光强度顺序为：Eu(DBM)_3dpq＞Eu(DBM)_3dpmq＞Eu(DBM)_3dptp＞Eu(DBM)_3dppz＞Eu(DBM)_3dpmp；Eu(TTA)_3dptp＞Eu(TTA)_3dpmq＞Eu(TTA)_3dppz＞Eu(TTA)_3dpq＞Eu(TTA)_3dpmp。
2．合成了五种新型酰亚胺类第一配体：L_1=2-(N-对甲基苯甲酰)-氨基-5-苯基-[1，3，4]-噁二唑，L_2=2-(N-对甲氧基苯甲酰)-氨基-5-苯基-[1，3，4]-噁二唑，L_3=2-(N-间吡啶甲酰)-氨基-5-苯基-[1，3，4]-噁二唑，L_4=2-(N-对吡啶甲酰)-氨基-5-苯基-[1，3，4]-噁二唑，L_5=2-[N-(β-萘甲酰)]-氨基-5-苯基-[1，3，4]-噁二唑。用此类化合物作第一配体1，10-菲咯啉作第二配体，合成了五个铕(Ⅲ)三元配合物。对Eu(L_2)_3Phen和Eu(L_3)_3Phen的晶体结构测定结果表明：第一配体通过羰基氧原子和其中一个噁二唑环上的氮原子与铕(Ⅲ)离子配位，形成八配位的扭曲四方反棱柱构型，配合物分子间存在弱的π-π作用。这些配合物都表现为铕(Ⅲ)离子特征发射，PL强度随芳基的不同而变化：Eu(L_4)_3Phen＞Eu(L_3)_3Phen＞Eu(L_5)_3Phen＞Eu(L_2)_3Phen＞Eu(L_1)_3Phen。
郑州大学硕士毕业论文
3.用Eu(DBM)3L(DBM是二苯甲酞甲烷，L是氮杂菲类配体)作为发光
材料制备了五个三层EL器件，器件结构为ITO厅PD(3 Onln)/铺配合物:仰D(1:2)
(50 nm)/Gd(DBM)3 bath(30 nm刃Mg:Ag。当发光材料为Eu(DBM)3dPq、
Eu(DBM)3dPmq和Eu但BM)3dPtp时，器件的EL光谱为铺(111)离子特征发射，
最高亮度分别为304ed/m“、n2.2 cd/mZ和122.4 cd/m“;当发光材料为
Eu(DBM)3dppz和Eu(DBM)3dpmp时，器件的EL光谱中除铺(111)离子发射外，
在600 nm附近还有一个宽的发射峰，器件的最大亮度分别为280 cd/m2和312
cd/mZ。
In order to obtain the excellent photo and electro-luminescent lanthanide complexes, Two series of new Eu(III) complexes with azatriphenylenes as the second ligand and imide as the first ligand were prepared in this parper. The structure characters and PL properties of these complexes were fully described. The three-layer EL diodes were prepared using Eu(DBM)3L as emitting material, their EL properties were described briefly.
1. Five azatriphenylenes ligands: dipyrido [2,3-a:2',3'-c] quinoxaline(dpq)
7-methyl-dipyrido[2,3-a:2',3'-c]quinoxaline(dpmq) dipyrido[2,3-a:2',3'-c]phenazine
(dppz) 8-methyl-dipyrido[2,3-a:2',3'-c]phenazine(dpmp) and dipyrido[2,3-a:2',3'-c] -7,8,9,10-tetraphenazine(dptp) were synthesized. Using these azatriphenylenes as the second ligands, DBM (dibenzoylmethane) and TTA (2-Thenoyltrifluoroacetone) as the first ligands ten new ternary Eu(IH) complexes were synthesized. The crystal analysis results of Eu(DBM)3 dpq, Eu(DBM)3 dppz and Eu(TTA)3 dpq indicated that Eu(III) ion is eight coordinated with six oxygen atoms from three first ligands and two nitrogen atoms from netural ligand, forming a distorted square antiprism. There are strong π-π stacking interaction between the adjacent complex molecules. Under UV excitation, all these complexes exhibit bright typical emission of Eu(III) ion, with the emission intensity decrease in the order: Eu(DBM)3 dpq > Eu(DBM)3dpmq > Eu(DBM)3dptp > Eu(DBM)3dppz > Eu(DBM)3dpmp; Eu(TTA)3dptp >
Eu(TTA)3dpmq > Eu(TTA)3dppz > Eu(TTA)3dpq > Eu(TTA)3dpmp.
2. Five new imide ligands: 4-Methyl-N-(5-phenyl-[l,3,4]oxadiazol-l-yl)-benzamide(L1) 4-Methoxy-N-(5-phenyl-[1,3,4]oxadiazol-1-yl)- benzamide(L2) N-(5-phenyl-[1,3,4]oxadiazol-l-yl)- nicotinamide N-(5-phenyl-[1,3,4]oxadiazol-1-yl)-isonicotinamide and Naphthalene-1-caroxylic acid(5-phenyl-[1,3,4]oxadiazol-2-yl)-amide were synthesized. Using these imides as first ligand and 1,10-phenanthroline as second ligand five new ternary Eu(III) complexes were prepared. The crystal analysis
results of Eu(L(2)3phen and Eu(L3)3phen indicated that imide Iigands coordinates with Eu(III) ion through the oxygen atom of the carbonyl group in the enol form, and the nitrogen atom of the oxadizol group. The coordinate polyhedron of Eu(III) ion is a distorted square antiprism. All these complexes exhibit typical emission of Eu(III) ion and the PL intensity vary with different aryl in first Iigands with the sequence Eu(L4)3Phen > Eu(L3)3Phen > Eu(L5)3Phen > Eu(L2)3Phen > Eu(Li)3Phen.
3. Using Eu(DBM)3L (L=azatriphenylene) as emitting materials five three-layer EL devices with the configuration of ITO/TPD (30 nm)/ europium complex :TPD(1:2) (50 nm)/Gd(DBM)3bath(30 nm)/Mg:Ag were prepared. The devices with Eu(DBM)3dpq Eu(DBM)3dpmq and Eu(DBM)3dptp as emitting material exhibit the characteristic emission of Eu(III) ion, the maximum EL brightness are 304 cd/m2 112.2 cd/m2 and 122.4 cd/m2 respectly; Devices with Eu(DBM)3dppz and Eu(DBM)adpmp as emitting material show a wide emission band aside from the Eu(III) ion emission, the maximum EL brightness are 280 cd/m2 and 312 cd/m2 respectly.
1．合成了五种氮杂菲类第二配体：二吡啶并[2，3-a：2′，3′-c]喹喔啉(dpq)、二吡啶并[2，3-a：2′，3′-c]-7-甲基-喹喔啉(dpmq)、二吡啶并[2，3-a：2′，3′-c]吩嗪(dppz)、二吡啶并[2，3-a：2′，3′-c]-8-甲基-吩嗪(dpmp)和二吡啶并[2，3-a：2′，3′-c]-7，8，9，10-四氢吩嗪(dptp)。用此类配体作第二配体，二苯甲酰甲烷(DBM)和2-噻吩甲酰三氟丙酮(TTA)作第一配体合成了十个铕(Ⅲ)三元配合物。用X-射线衍射发测定了Eu(DBM)_3 dpq、Eu(DBM)_3 dppz和Eu(TTA)_3dpq三种配合物的单晶结构，其中的铕(Ⅲ)离子均表现为八配位的扭曲四方反棱柱构型，配合物分子间都存在较强的π-π相互作用。在紫外光激发下，配合物均表现为较强的铕(Ⅲ)离子特征发射，不同配合物发光强度顺序为：Eu(DBM)_3dpq＞Eu(DBM)_3dpmq＞Eu(DBM)_3dptp＞Eu(DBM)_3dppz＞Eu(DBM)_3dpmp；Eu(TTA)_3dptp＞Eu(TTA)_3dpmq＞Eu(TTA)_3dppz＞Eu(TTA)_3dpq＞Eu(TTA)_3dpmp。
2．合成了五种新型酰亚胺类第一配体：L_1=2-(N-对甲基苯甲酰)-氨基-5-苯基-[1，3，4]-噁二唑，L_2=2-(N-对甲氧基苯甲酰)-氨基-5-苯基-[1，3，4]-噁二唑，L_3=2-(N-间吡啶甲酰)-氨基-5-苯基-[1，3，4]-噁二唑，L_4=2-(N-对吡啶甲酰)-氨基-5-苯基-[1，3，4]-噁二唑，L_5=2-[N-(β-萘甲酰)]-氨基-5-苯基-[1，3，4]-噁二唑。用此类化合物作第一配体1，10-菲咯啉作第二配体，合成了五个铕(Ⅲ)三元配合物。对Eu(L_2)_3Phen和Eu(L_3)_3Phen的晶体结构测定结果表明：第一配体通过羰基氧原子和其中一个噁二唑环上的氮原子与铕(Ⅲ)离子配位，形成八配位的扭曲四方反棱柱构型，配合物分子间存在弱的π-π作用。这些配合物都表现为铕(Ⅲ)离子特征发射，PL强度随芳基的不同而变化：Eu(L_4)_3Phen＞Eu(L_3)_3Phen＞Eu(L_5)_3Phen＞Eu(L_2)_3Phen＞Eu(L_1)_3Phen。
郑州大学硕士毕业论文
3.用Eu(DBM)3L(DBM是二苯甲酞甲烷，L是氮杂菲类配体)作为发光
材料制备了五个三层EL器件，器件结构为ITO厅PD(3 Onln)/铺配合物:仰D(1:2)
(50 nm)/Gd(DBM)3 bath(30 nm刃Mg:Ag。当发光材料为Eu(DBM)3dPq、
Eu(DBM)3dPmq和Eu但BM)3dPtp时，器件的EL光谱为铺(111)离子特征发射，
最高亮度分别为304ed/m“、n2.2 cd/mZ和122.4 cd/m“;当发光材料为
Eu(DBM)3dppz和Eu(DBM)3dpmp时，器件的EL光谱中除铺(111)离子发射外，
在600 nm附近还有一个宽的发射峰，器件的最大亮度分别为280 cd/m2和312
cd/mZ。
In order to obtain the excellent photo and electro-luminescent lanthanide complexes, Two series of new Eu(III) complexes with azatriphenylenes as the second ligand and imide as the first ligand were prepared in this parper. The structure characters and PL properties of these complexes were fully described. The three-layer EL diodes were prepared using Eu(DBM)3L as emitting material, their EL properties were described briefly.
1. Five azatriphenylenes ligands: dipyrido [2,3-a:2',3'-c] quinoxaline(dpq)
7-methyl-dipyrido[2,3-a:2',3'-c]quinoxaline(dpmq) dipyrido[2,3-a:2',3'-c]phenazine
(dppz) 8-methyl-dipyrido[2,3-a:2',3'-c]phenazine(dpmp) and dipyrido[2,3-a:2',3'-c] -7,8,9,10-tetraphenazine(dptp) were synthesized. Using these azatriphenylenes as the second ligands, DBM (dibenzoylmethane) and TTA (2-Thenoyltrifluoroacetone) as the first ligands ten new ternary Eu(IH) complexes were synthesized. The crystal analysis results of Eu(DBM)3 dpq, Eu(DBM)3 dppz and Eu(TTA)3 dpq indicated that Eu(III) ion is eight coordinated with six oxygen atoms from three first ligands and two nitrogen atoms from netural ligand, forming a distorted square antiprism. There are strong π-π stacking interaction between the adjacent complex molecules. Under UV excitation, all these complexes exhibit bright typical emission of Eu(III) ion, with the emission intensity decrease in the order: Eu(DBM)3 dpq > Eu(DBM)3dpmq > Eu(DBM)3dptp > Eu(DBM)3dppz > Eu(DBM)3dpmp; Eu(TTA)3dptp >
Eu(TTA)3dpmq > Eu(TTA)3dppz > Eu(TTA)3dpq > Eu(TTA)3dpmp.
2. Five new imide ligands: 4-Methyl-N-(5-phenyl-[l,3,4]oxadiazol-l-yl)-benzamide(L1) 4-Methoxy-N-(5-phenyl-[1,3,4]oxadiazol-1-yl)- benzamide(L2) N-(5-phenyl-[1,3,4]oxadiazol-l-yl)- nicotinamide N-(5-phenyl-[1,3,4]oxadiazol-1-yl)-isonicotinamide and Naphthalene-1-caroxylic acid(5-phenyl-[1,3,4]oxadiazol-2-yl)-amide were synthesized. Using these imides as first ligand and 1,10-phenanthroline as second ligand five new ternary Eu(III) complexes were prepared. The crystal analysis
results of Eu(L(2)3phen and Eu(L3)3phen indicated that imide Iigands coordinates with Eu(III) ion through the oxygen atom of the carbonyl group in the enol form, and the nitrogen atom of the oxadizol group. The coordinate polyhedron of Eu(III) ion is a distorted square antiprism. All these complexes exhibit typical emission of Eu(III) ion and the PL intensity vary with different aryl in first Iigands with the sequence Eu(L4)3Phen > Eu(L3)3Phen > Eu(L5)3Phen > Eu(L2)3Phen > Eu(Li)3Phen.
3. Using Eu(DBM)3L (L=azatriphenylene) as emitting materials five three-layer EL devices with the configuration of ITO/TPD (30 nm)/ europium complex :TPD(1:2) (50 nm)/Gd(DBM)3bath(30 nm)/Mg:Ag were prepared. The devices with Eu(DBM)3dpq Eu(DBM)3dpmq and Eu(DBM)3dptp as emitting material exhibit the characteristic emission of Eu(III) ion, the maximum EL brightness are 304 cd/m2 112.2 cd/m2 and 122.4 cd/m2 respectly; Devices with Eu(DBM)3dppz and Eu(DBM)adpmp as emitting material show a wide emission band aside from the Eu(III) ion emission, the maximum EL brightness are 280 cd/m2 and 312 cd/m2 respectly.
引文
[1] 李文连，中国稀土学报，1999，17，267．
[2] W L Li, Z Q Gao, Z Y Hong, C S Lee, S T Lee, Synth. Met., 2000, 111-112, 53.
[3] Choppin G R, Peterman D R, Coord. Chem. Rev., 1998, 174, 283.
[4] 李文连，化学通报，1991，8，1．
[5] 李红玉，于贵，刘云圻，王明昭，金林培，朱道本，稀土，2000，214，61．
[6] Junji Kido, Koshi Okamoto, Chem. Rev., 2002, 102, 2357.
[7] S.I. Weissman, J. Chem. Phys., 1942, 10, 214.
[8] G.A. Crosby, R.E. Whan, R.M. Alire, J. Chem. Phys., 1961, 34, 743.
[9] 傅楚瑾，曹锦荣，王则民，上海师范大学学报(自然科学版)，1992，21，54．
[10] 杨燕生，安保礼，龚孟濂，中国稀土学报，2001，19，298．
[11] 侯经国，杨迟，康敬万，高锦章，西北师范大学学报(自然科学版)，1996，32．113．
[12] Okamoto Y. Ueba Y, Dzhanibekov N F, Macromolecules, 1980, 14, 17.
[13] Ling Huang, Ke-Zhi Huang, Chun-Hui Huang, Fu-You Li and Yan-Li Huang, J. Mater. Chem., 2001,11,790.
[14] 成义祥，徐端钧，徐元植，无机化学学报，1998，14，181．
[15] Richardson F S, Chem. Rev., 1982, 82, 541.
[16] B.H. Bakker, M. Goes, N. Hoebe, H. Jo van Ramesdonk, J. W. Verhoeven, Coord. Chem. Rev., 2000, 208, 3.
[17] 陶建清，庄金钟，余智，游效曾，无机化学学报，2002，18，255．
[18] B.D. Alleyne, L. A. Hall, I.A. Kahwa, D. J. Williams, Inorg. Chem., 1999, 38, 6278.
[19] Zhu, L.-G., Chem. J. Chin. Univ., 2001, 22, 188.
[20] 侯彦辉，杜晨霞，朱玉，周稚仙，化学学报，2003，61，367．
[21] Bert D. Alleyne, Lincoln A. Hall, Ishenkumba A. Kahwa, Andrew J. P. White, David J. Williams, Inorg.Chem., 1999, 38, 6278.
[22] 苏锵，稀土化学 (河南科技出版社)，1993．
[23] Stephen I. Klink, Gerald A. Hebbink, Lennart Grave, Patrick G. B. Oude Alink, J. Phys. Chem.A, 2002, 106, 3685.
[24] 王利亚，金林培，北京师范大学学报，1998，34，378．
[25] 李林书，王瑞芬，金林培，蔡冠梁，高等学校化学学报，1995，16，501．
[26] 张颖，金林培，吕少哲，中国稀土学报，1998，16，7．
[27] M.S. Gibson, Tetrahedron, 1962, 18, 1377.
[28] 魏兆杰，李标国，黄春辉，高等学校化学学报，1995，16，172．
[29] Deqing Gao, Zuqiang Bian, Kezhi Wang, Chunhui Huang, J. Alloys. Compd. 2003, 358, 188.
[2] W L Li, Z Q Gao, Z Y Hong, C S Lee, S T Lee, Synth. Met., 2000, 111-112, 53.
[3] Choppin G R, Peterman D R, Coord. Chem. Rev., 1998, 174, 283.
[4] 李文连，化学通报，1991，8，1．
[5] 李红玉，于贵，刘云圻，王明昭，金林培，朱道本，稀土，2000，214，61．
[6] Junji Kido, Koshi Okamoto, Chem. Rev., 2002, 102, 2357.
[7] S.I. Weissman, J. Chem. Phys., 1942, 10, 214.
[8] G.A. Crosby, R.E. Whan, R.M. Alire, J. Chem. Phys., 1961, 34, 743.
[9] 傅楚瑾，曹锦荣，王则民，上海师范大学学报(自然科学版)，1992，21，54．
[10] 杨燕生，安保礼，龚孟濂，中国稀土学报，2001，19，298．
[11] 侯经国，杨迟，康敬万，高锦章，西北师范大学学报(自然科学版)，1996，32．113．
[12] Okamoto Y. Ueba Y, Dzhanibekov N F, Macromolecules, 1980, 14, 17.
[13] Ling Huang, Ke-Zhi Huang, Chun-Hui Huang, Fu-You Li and Yan-Li Huang, J. Mater. Chem., 2001,11,790.
[14] 成义祥，徐端钧，徐元植，无机化学学报，1998，14，181．
[15] Richardson F S, Chem. Rev., 1982, 82, 541.
[16] B.H. Bakker, M. Goes, N. Hoebe, H. Jo van Ramesdonk, J. W. Verhoeven, Coord. Chem. Rev., 2000, 208, 3.
[17] 陶建清，庄金钟，余智，游效曾，无机化学学报，2002，18，255．
[18] B.D. Alleyne, L. A. Hall, I.A. Kahwa, D. J. Williams, Inorg. Chem., 1999, 38, 6278.
[19] Zhu, L.-G., Chem. J. Chin. Univ., 2001, 22, 188.
[20] 侯彦辉，杜晨霞，朱玉，周稚仙，化学学报，2003，61，367．
[21] Bert D. Alleyne, Lincoln A. Hall, Ishenkumba A. Kahwa, Andrew J. P. White, David J. Williams, Inorg.Chem., 1999, 38, 6278.
[22] 苏锵，稀土化学 (河南科技出版社)，1993．
[23] Stephen I. Klink, Gerald A. Hebbink, Lennart Grave, Patrick G. B. Oude Alink, J. Phys. Chem.A, 2002, 106, 3685.
[24] 王利亚，金林培，北京师范大学学报，1998，34，378．
[25] 李林书，王瑞芬，金林培，蔡冠梁，高等学校化学学报，1995，16，501．
[26] 张颖，金林培，吕少哲，中国稀土学报，1998，16，7．
[27] M.S. Gibson, Tetrahedron, 1962, 18, 1377.
[28] 魏兆杰，李标国，黄春辉，高等学校化学学报，1995，16，172．
[29] Deqing Gao, Zuqiang Bian, Kezhi Wang, Chunhui Huang, J. Alloys. Compd. 2003, 358, 188.