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

doi:10.6023/A12090695

Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (24): 2501-2506.DOI: 10.6023/A12090695 Previous Articles Next Articles

Article

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.

1. Syntheses, Characterization and Fluorescent Properties of Lanthanide-Containing Ionic Liquids [C_nmim][Ln(NO₃)₄].PDF(164KB)

Abstract

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

Cite this article

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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含稀土离子液体[Cnmim][Ln(NO3)4]的合成、表征及荧光性能研究