含稀土离子液体[Cnmim][Ln(NO3)4]的合成、表征及荧光性能研究

doi:10.6023/A12090695

化学学报 ›› 2012, Vol. 70 ›› Issue (24): 2501-2506.DOI: 10.6023/A12090695 上一篇下一篇

研究论文

含稀土离子液体[C_nmim][Ln(NO₃)₄]的合成、表征及荧光性能研究

顾志国^a,b, 王宝祥^a, 庞春燕^a, 周文^a, 李在均^a

a 江南大学化学与材料工程学院无锡 214122;
b 南京大学配位化学国家重点实验室南京 210093

投稿日期:2012-09-21 发布日期:2012-11-29
通讯作者: 顾志国 E-mail:zhiguogu@jiangnan.edu.cn
基金资助:
项目受国家自然科学基金(No. 21101078)、新世纪优秀人才计划(No. NCET-11-0657)、江苏省自然科学基金(No. BK2011143)、中央高校基本科研业务费专项资金(No. JUSRP21111)和南京大学配位化学国家重点实验室开放基金资助.

Syntheses, Characterization and Fluorescent Properties of Lanthanide-Containing Ionic Liquids [C_nmim][Ln(NO₃)₄]

Gu Zhiguo^a,b, Wang Baoxiang^a, Pang Chunyan^a, Zhou Wen^a, Li Zaijun^a

a School of Chemistry and Material Engineering, Jiangnan University, Wuxi 214122;
b State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093

Received:2012-09-21 Published:2012-11-29
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21101078), the Program for New Century Excellent Talents in University of China (No. NCET-11-0657), the Natural Science Foundation of Jiangsu Province (No. BK2011143), the Fundamental Research Funds for the Central Universities (No. JUSRP21111) and the State Key Laboratory of Coordination Chemistry of Nanjing University.

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1. 含稀土离子液体[C_nmim][Ln(NO₃)₄]的合成、表征及荧光性能研究.PDF(164KB)

摘要/Abstract

以N-甲基咪唑, 溴代烷烃和硝酸钠为原料, 合成了5种离子液体[C_nmim]NO₃ (n＝2, 4, 6, 8, 10; mim＝N-甲基咪唑), 并对离子液体进行了表征. 用[C_nmim]NO₃与硝酸铕、硝酸铽反应, 得到了含稀土离子液体[C_nmim][Ln(NO₃)₄] (Ln＝Eu, Tb). 利用电喷雾质谱对[C_nmim][Ln(NO₃)₄]的结构进行了表征, 结果表明稀土离子与来自4个硝酸根的8个氧原子配位, 形成[Ln(NO₃)₄]^-阴离子, 阳离子为1-烷基-3-甲基咪唑. 荧光研究表明, [C_nmim][Ln(NO₃)₄] (Ln＝Eu, Tb)的溶液存在较强荧光; 温度和浓度影响荧光强度.

关键词: 离子液体, 稀土, 合成, 表征, 荧光

Five kinds of ionic liquids 1-alkyl-3-methylimidazolium nitrate [C_nmim]NO₃ (n＝2, 4, 6, 8, 10; mim＝N-methylimidazolium) were synthesized from N-methylimidazolium, alkyl bromides and sodium nitrate. The structures of ionic liquids were characterized and analyzed by infrared spectra (IR), proton nuclear magnetic resonance (¹H NMR), mass spectrometry (MS) and elemental analyses (EA). Lanthanide-containing ionic liquids [C_nmim][Ln(NO₃)₄] (Ln＝Eu, Tb) were prepared by reactions of 1-alkyl-3-methylimidazolium nitrate and europium nitrate/terbium nitrate in 1∶1 molar ratio. [C_nmim][Ln(NO₃)₄] were all sticky liquids at room temperature. The strength of nitrate absorption peaks of [C_nmim][Ln(NO₃)₄] in the IR spectra was stronger than [C_nmim]NO₃ which indicated that the coordination of nitrate anions to lanthanide ions enhanced the nitrate absorption peaks. The structures of [C_nmim][Ln(NO₃)₄] contained 1-alkyl-3-methylimidazolium cations and [Ln(NO₃)₄]^- anions in which each lanthanide ion was coordinated with eight oxygen atoms from four nitrate ions were further confirmed by ESI mass spectrometry. The thermal decomposition of [C_nmim]NO₃ and [C_nmim][Ln(NO₃)₄] were investigated by thermogravimetric analysis (TGA), which indicated that all the compounds represented high stability until ca. 250 ℃. Under UV lamp irradiated at 365 nm, [C_nmim][Eu(NO₃)₄] and [C_nmim][Tb(NO₃)₄] showed red and green fluorescence, respectively, which indicated that these lanthanide-containing ionic liquids could be used as good soft luminescent materials. The photoluminescence properties of the lanthanide-containing ionic liquids were studied at room temperature in water by measuring emission and excitation spectra. These experiments demonstrated that the solution of [C_nmim][Ln(NO₃)₄] (Ln＝Eu, Tb) showed strong characteristic fluorescence. The red fluorescence of [C_nmim][Eu(NO₃)₄] was assigned to Eu³⁺ ⁵D₀-⁷F₂transition at 617 nm, while the green fluorescence of [C_nmim][Tb(NO₃)₄] was assigned to Tb³⁺ ⁵D₄-⁷F₅transition at 545 nm. Temperature and concentration influenced the solution fluorescence intensity of [C_nmim][Ln(NO₃)₄]. Due to the intermolecular collision intensified in solution with temperature increasing, the fluorescence intensity of [C_nmim][Ln(NO₃)₄] decreased. Fluorescence intensity increased with the concentration increasing, while fluorescence quenching phenomenon appeared when exceeded a certain concentration.

Key words: ionic liquids, lanthanide, syntheses, characterization, fluorescence

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顾志国, 王宝祥, 庞春燕, 周文, 李在均. 含稀土离子液体[C_nmim][Ln(NO₃)₄]的合成、表征及荧光性能研究[J]. 化学学报, 2012, 70(24): 2501-2506.

Gu Zhiguo, Wang Baoxiang, Pang Chunyan, Zhou Wen, Li Zaijun. Syntheses, Characterization and Fluorescent Properties of Lanthanide-Containing Ionic Liquids [C_nmim][Ln(NO₃)₄][J]. Acta Chimica Sinica, 2012, 70(24): 2501-2506.

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含稀土离子液体[C_nmim][Ln(NO₃)₄]的合成、表征及荧光性能研究

Syntheses, Characterization and Fluorescent Properties of Lanthanide-Containing Ionic Liquids [C_nmim][Ln(NO₃)₄]

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