铕-2-羟基喹啉-4-羧酸配合物的合成及光谱性能
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摘要
以Eu3+为中心离子,2-羟基喹啉-4-羧酸(H2hqc)、1,10-菲罗啉(Phen)和三苯基氧磷(TPPO)为配体,合成了新型配合Eu(Hhqc)3(H2O)、Eu(Hhqc)3Phen(H2O)5和Eu(Hhqc)3TPPO(H2O)5.用元素分析和红外光谱对配合物进行了表征,IR表明配合物Eu(Hhqc)3Phen(H2O)5的Δν值大于钠盐Δν值,配合物中羧酸根以单齿方式配位.而配合物Eu(Hhqc)3(H2O)和Eu(Hhqc)3TPPO(H2O)5Δν值均小于钠盐的Δν值,表明配合物中羧酸根与Eu3+呈螯合双齿配位方式.室温下测定了配合物的荧光光谱,研究了它们的荧光性能.结果表明,配合物均在581,594,615,654和703nm附近产生五条谱带,为Eu3+的特征发射,归属为5 D0→7 FJ(J=0,1,2,3,4)能级间的跃迁,第二配体Phen和TPPO的引入对Eu3+的荧光发射有明显增强作用,且Phen效果更好.
Three novel europium complexes,Eu(Hhqc)3(H2O),Eu(Hhqc)3Phen(H2O)5 and Eu(Hhqc)3TPPO(H2O)5 were synthesized using 2-Hydroxyquinoline-4-carboxylic acid(H2hqc),1,10-phenanthroline(Phen)and triphenyl phosphine oxide(TPPO)as the ligands.The complexes were characterized by elemental analysis and infrared spectrum.The IR spectra indicated that the complex Eu(Hhqc)3Phen(H2O)5 has a largerΔνthan that of NaHhqc,and carboxylate ions in the phenylglyoxyate are coordinated as monodentate ligands.TheΔνvalues of the Eu(Hhqc)3(H2O)and Eu(Hhqc)3TPPO-(H2O)5 are smaller than that of NaHhqc,the carboxylate ions coordinate to Eu3+ with bidentate chelating mode.The fluorescence properties of the complexes were studied at room temperature.Each complex shows five emission bands at 581,594,615,654 and 703nm,which are assigned to the characteristic emission 5D0→7FJ(J=0,1,2,3,4)transitions of Eu3+,respectively.The fluorescence intensity becomes stronger after the additions of Phen and TPPO,and Phen is better.
Three novel europium complexes,Eu(Hhqc)3(H2O),Eu(Hhqc)3Phen(H2O)5 and Eu(Hhqc)3TPPO(H2O)5 were synthesized using 2-Hydroxyquinoline-4-carboxylic acid(H2hqc),1,10-phenanthroline(Phen)and triphenyl phosphine oxide(TPPO)as the ligands.The complexes were characterized by elemental analysis and infrared spectrum.The IR spectra indicated that the complex Eu(Hhqc)3Phen(H2O)5 has a largerΔνthan that of NaHhqc,and carboxylate ions in the phenylglyoxyate are coordinated as monodentate ligands.TheΔνvalues of the Eu(Hhqc)3(H2O)and Eu(Hhqc)3TPPO-(H2O)5 are smaller than that of NaHhqc,the carboxylate ions coordinate to Eu3+ with bidentate chelating mode.The fluorescence properties of the complexes were studied at room temperature.Each complex shows five emission bands at 581,594,615,654 and 703nm,which are assigned to the characteristic emission 5D0→7FJ(J=0,1,2,3,4)transitions of Eu3+,respectively.The fluorescence intensity becomes stronger after the additions of Phen and TPPO,and Phen is better.
引文
[1]Khreis O M,Curry R J,Somertom M,et al.Infrared organic light emitting devices using neodymium tris-(8-hydrooxyquoline)[J].J.Appl.Phys.,2000,88(1):777.
[2]Li W L.Progress on rare earth organic electroluminescence[J].Chin.J.Rare Earth,1999,17(3):267(in Chinese)[李文连.稀土有机电致发光研究进展[J].中国稀土学报,1999,17(3):267]
[3]Xu J,Liu W S,Tang Y.Research progress on the assembly and photophysical properties of hybrid luminescent materials based on rare earth complexes[J].Scientia Sinica Chimica,2013,43(10):1272(in Chinese)[徐君,刘伟生,唐瑜.稀土配合物杂化发光材料的组装及光物理性质研究进展[J].中国科学,2013,43(10):1272]
[4]Su M Y,Liu L L,Sun T.Synthesis and fluorescence spectrum of the Eu complex and the Eu-L(L=La,Y,Yb and Nd)complex with 1,2-phenylenedioxydiacetic acid and dibenzoylmethane[J].J.Mol.Sci.,2012,28(3):227(in Chinese)[苏明月,刘连利,孙彤.1,2-邻苯二氧基二乙酸铕及掺杂L(L=La,Y,Yb,Nd)配合物的合成及荧光性质研究[J].分子科学学报,2012,28(3):227]
[5]Yuan G.Syntheses,crystal structures and properties of coordination polymers constructed from 2-hydroxyquinoline-4-carboxylic acid and 1 H-1,2,3-triazole-4,5-dicarboxylic acid[D].Jilin:Northeast Normal University,2009(in Chinese)[袁刚.2-羟基喹啉-4-羧酸和1,2,3-三唑-4,5-二羧酸构筑的配位聚合物的合成、结构及性质[D].吉林:东北师范大学,2009]
[6]Zhang Y H,Hao Y Z,Pei J,et al.Synthesis and fluorescence properties of europium complexes with4-(4-pyridyl formoyl)benzoic acid[J].Spectrosc Spect Anal.,2011,31(1):146(in Chinese)[张彦辉,郝彦忠,裴娟,等.铕与4-(4-吡啶甲酰基)苯甲酸配合物的合成与荧光性能研究[J].光谱学与光谱分析,2011,31(1):146]
[7]Zhao Y L,Zhao F Y.Study on infrared and fluorescence spectra of Eu(La)complexes with o-phenanthroline and p-phthalic acid[J].Chin.J.Rare Earth,2001,19(5):398(in Chinese)[赵永亮,赵凤英.对-苯二甲酸邻菲罗啉铕镧配合物的红外光谱及荧光光谱研究[J].中国稀土学报,2001,19(5):398]
[8]Xu C J,Shi Y Q.Synthesis and luminescence properties of a reactive ternary europium complex containing 1,10-phenanthroline[J].Spectrosc Spect Anal.,2013,33(1):117(in Chinese)[徐存进,施燕琴.基于邻菲咯啉的反应型三元铕配合物的合成与荧光性质[J].光谱学与光谱分析,2013,33(1):117]
[9]Wei J Q,Sun C,Huang L Q.Application of rare earth europium complexes in fluorescent falsification-resistant ink[J].J.Tianjin Univ.Sci.&Tech.,2012,27(4):38(in Chinese)[魏俊青,孙诚,黄利强.稀土铕配合物在荧光防伪油墨中的应用[J].天津科技大学学报,2012,27(4):38]
[10]Zhang J,Wang J F,Zang J J.Synthesis characterization and thermal decomposition mechanism of rare earth complexes with 5-chloro-2-methoxybenzoic acid and 1,10-phenanthroline[J].Acta.PhysChim.Sin.,2012,28(2):292(in Chinese)[张洁,王娟芬,张建军.5-氯-2-甲氧基苯甲酸与1,10-邻菲啰啉稀土配合物的合成、表征及热分解机理[J].物理化学学报,2012,28(2):292]
[11]Li S K,Yan L,Zhao J S.Synthesis characterization and fluorescence properties of rare earth(Eu,Dy,Pr)complexes[J].Chin.Rare Earths,2012,33(6):7(in Chinese)[李淑开,颜莉,赵吉寿.稀土(Eu,Dy,Pr)配合物合成、表征及荧光性质[J].稀土,2012,33(6):7]
[12]Lu Z J,Wei C P,Ren X M,et al.Synthesis and fluorescence property of novel rare earth europium’terbium(Ⅲ)ternary complexes with aromatic carboxylic acid[J].Chin.J.Rare Earth,2012,30(4):412(in Chinese)[吕志军,魏长平,任晓明,等.新型稀土Eu,Tb(Ⅲ)芳香羧酸配合物的合成及发光性能[J].中国稀土学报,2012,30(4):412]
[13]Liu M Z,Yang Z L,Zhang L,et al.Photoluminescence of solid complexes EuxM1-x(TTA)3(H2O)2(M=La,Gd)[J].Acta Phys-Chim.Sin.,2001,17(9):797(in Chinese)[刘铭钊,杨展澜,张莉,等.配合物EuxM1-x(TTA)3(H2O)2(M=La,Gd)光致发光特性[J].物理化学学报,2001,17(9):797]
[14]Klink S I,Grave L,Reinhoudt D N,et al.A systematic study of the photophysical processes in polydentate triphenylene-functionalized Eu3+,Tb3+,Nd3+,Yb3+,and Er3+complexes[J].J.Phys.Chem.A,2000,104:5457.
[2]Li W L.Progress on rare earth organic electroluminescence[J].Chin.J.Rare Earth,1999,17(3):267(in Chinese)[李文连.稀土有机电致发光研究进展[J].中国稀土学报,1999,17(3):267]
[3]Xu J,Liu W S,Tang Y.Research progress on the assembly and photophysical properties of hybrid luminescent materials based on rare earth complexes[J].Scientia Sinica Chimica,2013,43(10):1272(in Chinese)[徐君,刘伟生,唐瑜.稀土配合物杂化发光材料的组装及光物理性质研究进展[J].中国科学,2013,43(10):1272]
[4]Su M Y,Liu L L,Sun T.Synthesis and fluorescence spectrum of the Eu complex and the Eu-L(L=La,Y,Yb and Nd)complex with 1,2-phenylenedioxydiacetic acid and dibenzoylmethane[J].J.Mol.Sci.,2012,28(3):227(in Chinese)[苏明月,刘连利,孙彤.1,2-邻苯二氧基二乙酸铕及掺杂L(L=La,Y,Yb,Nd)配合物的合成及荧光性质研究[J].分子科学学报,2012,28(3):227]
[5]Yuan G.Syntheses,crystal structures and properties of coordination polymers constructed from 2-hydroxyquinoline-4-carboxylic acid and 1 H-1,2,3-triazole-4,5-dicarboxylic acid[D].Jilin:Northeast Normal University,2009(in Chinese)[袁刚.2-羟基喹啉-4-羧酸和1,2,3-三唑-4,5-二羧酸构筑的配位聚合物的合成、结构及性质[D].吉林:东北师范大学,2009]
[6]Zhang Y H,Hao Y Z,Pei J,et al.Synthesis and fluorescence properties of europium complexes with4-(4-pyridyl formoyl)benzoic acid[J].Spectrosc Spect Anal.,2011,31(1):146(in Chinese)[张彦辉,郝彦忠,裴娟,等.铕与4-(4-吡啶甲酰基)苯甲酸配合物的合成与荧光性能研究[J].光谱学与光谱分析,2011,31(1):146]
[7]Zhao Y L,Zhao F Y.Study on infrared and fluorescence spectra of Eu(La)complexes with o-phenanthroline and p-phthalic acid[J].Chin.J.Rare Earth,2001,19(5):398(in Chinese)[赵永亮,赵凤英.对-苯二甲酸邻菲罗啉铕镧配合物的红外光谱及荧光光谱研究[J].中国稀土学报,2001,19(5):398]
[8]Xu C J,Shi Y Q.Synthesis and luminescence properties of a reactive ternary europium complex containing 1,10-phenanthroline[J].Spectrosc Spect Anal.,2013,33(1):117(in Chinese)[徐存进,施燕琴.基于邻菲咯啉的反应型三元铕配合物的合成与荧光性质[J].光谱学与光谱分析,2013,33(1):117]
[9]Wei J Q,Sun C,Huang L Q.Application of rare earth europium complexes in fluorescent falsification-resistant ink[J].J.Tianjin Univ.Sci.&Tech.,2012,27(4):38(in Chinese)[魏俊青,孙诚,黄利强.稀土铕配合物在荧光防伪油墨中的应用[J].天津科技大学学报,2012,27(4):38]
[10]Zhang J,Wang J F,Zang J J.Synthesis characterization and thermal decomposition mechanism of rare earth complexes with 5-chloro-2-methoxybenzoic acid and 1,10-phenanthroline[J].Acta.PhysChim.Sin.,2012,28(2):292(in Chinese)[张洁,王娟芬,张建军.5-氯-2-甲氧基苯甲酸与1,10-邻菲啰啉稀土配合物的合成、表征及热分解机理[J].物理化学学报,2012,28(2):292]
[11]Li S K,Yan L,Zhao J S.Synthesis characterization and fluorescence properties of rare earth(Eu,Dy,Pr)complexes[J].Chin.Rare Earths,2012,33(6):7(in Chinese)[李淑开,颜莉,赵吉寿.稀土(Eu,Dy,Pr)配合物合成、表征及荧光性质[J].稀土,2012,33(6):7]
[12]Lu Z J,Wei C P,Ren X M,et al.Synthesis and fluorescence property of novel rare earth europium’terbium(Ⅲ)ternary complexes with aromatic carboxylic acid[J].Chin.J.Rare Earth,2012,30(4):412(in Chinese)[吕志军,魏长平,任晓明,等.新型稀土Eu,Tb(Ⅲ)芳香羧酸配合物的合成及发光性能[J].中国稀土学报,2012,30(4):412]
[13]Liu M Z,Yang Z L,Zhang L,et al.Photoluminescence of solid complexes EuxM1-x(TTA)3(H2O)2(M=La,Gd)[J].Acta Phys-Chim.Sin.,2001,17(9):797(in Chinese)[刘铭钊,杨展澜,张莉,等.配合物EuxM1-x(TTA)3(H2O)2(M=La,Gd)光致发光特性[J].物理化学学报,2001,17(9):797]
[14]Klink S I,Grave L,Reinhoudt D N,et al.A systematic study of the photophysical processes in polydentate triphenylene-functionalized Eu3+,Tb3+,Nd3+,Yb3+,and Er3+complexes[J].J.Phys.Chem.A,2000,104:5457.