硅烷改性邻苯二甲基酰氯和1,10-邻菲罗啉的铕(Ⅲ)配合物制备及荧光性质的研究
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摘要
稀土配合物有非常好的荧光性质,但简单的配合物由于较低光、热特性限制了其应用。以硅烷改性邻苯二甲基酰氯制备改性配体和1,10-邻菲罗啉,与硝酸铕的六水合物反应制备了一系列的铕三元配合物。研究不同反应条件下对铕配合物荧光强度的影响,确定了最佳反应时间、反应温度以及铕离子与两种配体的比例;通过红外光谱,紫外光谱及荧光光谱,推测了配合物的结构,探讨了其能量传递过程;通过热重分析仪测定了配合物的稳定性。结果表明,配比为1∶6∶1改性配合物表现出了更强的铕离子荧光特征峰,说明铕离子的第一激发态和改性配体及辅助配体的三重态能级之间有更强的匹配。
Rare earth complexes have great fluorescence properties,but simple complexes have limited their application due to lower light and structural characteristics. A series of ternary complexes were synthesized by the europium nitrate hexahydrate reacted with silane-modified phthaloyl chloride and auxiliary ligand 1,10-phenanthroline. The effects of different reaction conditions on the fluorescence intensity of europium complexes were studied,which can concluded that the optimum reaction time,reaction temperature and proportion of modified ligands. By analysing of the IR,UV and fluorescence spectrum,this provided a basis for further predicting the structure of complexes and discussing the energy transfer process. The stability of the complexes was determined by the thermogravimetric analyzer. The result showed that 1 ∶ 6 ∶ 1 modified complexes displayed characteristic Eu3+ion fluorescence and exhibited that the strongest characteristic fluorescence emission intensity. The first excited state of Eu3+ion with the triple state energy level of the modified ligands and auxiliary ligands have stronger matching.
Rare earth complexes have great fluorescence properties,but simple complexes have limited their application due to lower light and structural characteristics. A series of ternary complexes were synthesized by the europium nitrate hexahydrate reacted with silane-modified phthaloyl chloride and auxiliary ligand 1,10-phenanthroline. The effects of different reaction conditions on the fluorescence intensity of europium complexes were studied,which can concluded that the optimum reaction time,reaction temperature and proportion of modified ligands. By analysing of the IR,UV and fluorescence spectrum,this provided a basis for further predicting the structure of complexes and discussing the energy transfer process. The stability of the complexes was determined by the thermogravimetric analyzer. The result showed that 1 ∶ 6 ∶ 1 modified complexes displayed characteristic Eu3+ion fluorescence and exhibited that the strongest characteristic fluorescence emission intensity. The first excited state of Eu3+ion with the triple state energy level of the modified ligands and auxiliary ligands have stronger matching.
引文
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[3] Moore E G,Xu J,Jocher C J,et al. Cymothoe sangaris:an extremely stable and highly luminescent 1,2-hydroxypyridinonate chelate of Eu(III)[J]. Journal of the American Chemical Society,2006,(128):10648-10649.
[4] Shavaleev N M,Eliseeva S V,Scopelliti R,et al. Tridentate benzimidazole-pyridine-tetrazolates as sensitizers of europium luminescence[J]. Inorganic Chemistry,2014,53(10):5171-5178.
[5] Li X,Shen G,Jin X,et al. Novel polyimide containing1,10-phenanthroline and its europium(III)complex:synthesis,characterization,and luminescence properties[J]. Journal of Materials Science,2016,51(4):2072-2078.
[6] Li W X,Guo F,Zheng Y S,et al. Synthesis and luminescence properties of two novel europium(III)perchlorate complexes with bis(benzylsulfinyl)methane and 1,10-phenanthroline[J]. Journal of Luminescence,2014,153(3):421-429.
[7] Li W X,Li Y J,Chai W J,et al. Syntheses and fluorescence properties of two novel lanthanide(iii)perchlorate complexes with bis(benzylsulfinyl)methane[J]. Journal of Fluorescence,2012,22(2):651-658.
[8] Shavaleev N M,Eliseeva S V,Scopelliti R,et al. Influence of symmetry on the luminescence and radiative lifetime of nine-coordinate europium complexes.[J]. Inorganic Chemistry,2015,54(18):9166-9173.
[9] Li H F,Yan P F,Chen P,et al. Highly luminescent bis-diketone lanthanide complexes with triple-stranded dinuclear structure.[J]. Dalton Transactions,2012,41(3):900.
[10] Xu C J,Li B G,Wan J T,et al. Synthesis and characterization of a Eu-containing polymer precursor featuring thenoyltrifluoroacetone and 5-acrylamido-1,10-phenanthroline[J]. Spectrochimica Acta Part A Molecular&Biomolecular Spectroscopy,2011,82(1):159-163.
[11] Shen C Q,Yan T L,Wang Y T,et al. Synthesis,structure and luminescence properties of binary and ternary complexes of lanthanide(Eu3+,Sm3+,and Tb3+)with salicylic acid and 1,10-phenanthroline[J]. Journal of Luminescence,2017,184:48-54.
[12] Blanco I,Bottino F A,Abate L. Influence of n-alkyl substituents on the thermal behaviour of Polyhedral Oligomeric Silsesquioxanes(POSSs)with different cage's periphery[J]. Thermochimica Acta,2016,623:50-57.
[13] Guo M,ric David,Fréchette M,et al. Polyethylene/polyhedral oligomeric silsesquioxanes composites:Dielectric,thermal and rheological properties[J]. Polymer,2017,115:60-69.
[14]王芳芳,徐青景,王砥,等.氨基硅烷改性芳香二酰氯及其稀土配合物的制备与荧光性能[J].稀土,2016(5):12-17.Wang F F,Xu Q J,Wang D,et al. Preparation and luminescent properties of rare earth complexes coupling with aromatic chloride modified by amino silane[J].Chinese Rare Earths,2016,37(5):12-17.
[15]高继红,杨天林.系列Schiff配体及其Eu(Ⅲ),Tb(Ⅲ)配合物的合成、表征及荧光性质[J].稀土,2010,31(5):7-13.Gao J H,Yang T L. Synthesisi characterization and fluorescence of series schiff bases and their Eu(III)、Tb(III)complexes[J]. Chinese Rare Earths,2010,31(5):7-13.
[16]王正祥,舒万艮,周忠诚,等.铕-芳香族有机羧酸-邻菲罗啉配合物的合成和荧光性能的研究[J].稀有金属,2002,26(4):281-283.Wang Z X,Shu W L,Zhou Z C,et al. Synthesis and fluorescence studies on complexes of eu(iii)with aromatic carboxylic acid-1,10-phenanthroline[J]. Chinese Journal of Rare Metals,2002,26(4):281-283.
[17] Bala M,Kumar S,Devi R,et al. Synthesis,NMR,photoluminescence studies and intramolecular energy transfer process of europium(III)complexes[J]. Journal of Fluorine Chemistry,2015,178:6-13.