光谱学与光谱分析 |
|
|
|
|
|
Synthesis and Spectral Characterization of Ce(Ⅲ)and Dy(Ⅲ)Complexes with Tetraisopropylmethylenediphosphonate |
GAO Hong-wei1,DONG Jia-cui1,ZHAO Xing-e2,YANG Liang1,JIN Qiong-hua1* |
1. Department of Chemistry, Captial Normal University, Beijing 100037, China 2. Department of Chemistry,Xiangtan University, Xiangtan 411105, China |
|
|
Abstract Three rare-earth complexes [CeL4](OTf)3·2H2O(L=tetraisopropylmethylene -diphosphonate; OTf=trifluoromethanesulfate), [Dy(OTf)2L2(H2O)2](OTf)(CH3CN) and [DyL4](OTf)3·L·2H2O were prepared by the reaction of Ln(OTf)3(Ln=Ce,Dy) and (iPrO)2P(O)CH2P(O)(iPrO)2 in CH3CN. Their compositions were confirmed and their properties were characterized by elemental analysis, infrared spectra, 1H and 31P NMR spectroscopy, fluorescence spectra and DTA-TGA. The data of elemental analysis of these complexes are in good agreement with the formula given above. In the infrared spectra of all these complexes, there are obvious shifts of some important absorption bands, such as the PO or S—O bands, illustrating that the ligands L or OTf ions were coordinated to the lanthanide ions. The signals in 1H NMR spectrum at approximately 1.2, 2.4 and 4.5 have been assigned to the resonance of H atoms in the ligand L, and these signals in the spectrum of complexes are highfield shifted compared to that of free ligand due to the electron cloud of Ln—O band moving towards to P—O band. The sharp single peaks were found in the 31P NMR spectrum, and the chemical shifts are at 18.705 6 for free ligand L, 18.543 5 for complex Ⅰ, 18.273 1 for complex Ⅱ, and 18.489 4 for complex Ⅲ. The excitation and emission signals of Ce(Ⅲ) ion were in view of electric dipole transition from 4f15d1 to 4f7. The fluorescence spectroscopy shows that the excitation peak of [CeL4](OTf)3·2H2O is at 249 and 300 nm, and a strong emission peak is at 641 nm. The existence of two coordination water molecules in [Dy(OTf)2L2(H2O)2](OTf)(CH3CN) makes both the excitation and emission peaks weaker than that of [DyL4](OTf)3·L·2H2O. The coordination model of rare-earth with diphosphonic ligand was also discussed. All of these complexes are eight-coordinated. The complexes [CeL4](OTf)3·2H2O and [DyL4](OTf)3·L·2H2O are highly-symmetrical, in which four bidentate ligands L are coordinated to Ce and Dy atoms respectively while the OTf ions and the water molecules are not coordinated. In the complex [Dy(OTf)2L2(H2O)2](OTf)(CH3CN), two L molecules, two water molecules and two OTf ions are coordinated to Dy atom while one OTf ion and one solvent molecule CH3CN are not coordinated.
|
Received: 2007-06-06
Accepted: 2007-09-16
|
|
Corresponding Authors:
JIN Qiong-hua
E-mail: jinqh@mail.cnu.edu.cn
|
|
[1] XU Guang-xian(徐光宪). Rare Earth, 2nd Ed(稀土, 第2版). Beijing: Metallurgical Industry Press(北京:冶金工业出版社), 1995. 124. [2] HUANG Ling, HUANG Chun-hui(黄 玲, 黄春辉). Acta Chimica Sinica(化学学报), 2000, 58(12): 1493. [3] ZHANG Quan-ping, DU Hai-yan, SUN Jia-yue, et al(张泉平,杜海燕,孙家跃,等). New Chemical Materials(化工新型材料), 2006, 34(6): 1. [4] JIN Qiong-hua, Li Xia,Zou Ying-quan, et al. Zeitschft Fur kristallographie-New Crystal Structures, 2003, 218(1): 45. [5] LI Wen-xian, ZHANG Rui-ping, GUO Lei,et al(李文先, 张瑞平, 郭 磊,等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2007, 27(7): 1279. [6] BAO Jin-rong, ZHU Xiao-wei, WANG Zhi-liang, et al(宝金荣, 朱晓伟, 王智亮, 等). Chinese Journal of Rare Earths(稀土), 2007, 28(3): 38. [7] BAO Jin-rong, ZHAO Yong-liang, ZHU Xiao-wei(宝金荣, 赵永亮, 朱晓伟). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2007, 27(3): 539. [8] TANG Rui-ren, YAN Zi-er, GUO Can-cheng, et al(唐瑞仁, 严子耳, 郭灿城,等). Chemical Journal of Chinese Universities(高等学校化学学报), 2006, 27(3): 472. [9] SUN Wu-juan, GAO Xue-xiang, WANG Xiao-yan, et al(孙妩娟, 高学祥, 王小燕,等). Journal of Northwest University(Natural Science Edition)(西北大学学报·自然科学版), 2007, 37(3): 415. [10] JIN Qiong-hua, Ricard Louis, Nief Francois. Polyhedron, 2005, 24: 549. [11] Aspinall H C. Chem. Rev., 2002, 102: 1807. [12] John F, Andrew W G P, David R R. Polyhedron, 2002, 21: 287. [13] LIN Hai, LIN Jiu-ling, LIU Xing-ren(林 海,林久令,刘行人). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 1998, 18(6): 645. [14] WU Gen-hua, CHEN Rong, ZHANG Qi-yun(吴根华, 陈 荣, 张启运). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2000, 20(4): 560. [15] ZHU Xiao-wei, BU Ren, BAO Jin-rong(朱晓伟, 布 仁, 宝金荣). Chemical Reagent(化学试剂), 2007, 29(6): 361, 365. [16] JU Yan-ling, ZHANG Ting-ting, LI Xia(鞠艳玲, 张婷婷, 李 夏). Chinese Journal of Applied Chemistry(应用化学), 2006, 23(12): 1408. [17] YANG Rui, HE Shui-yang, WU Wang-ting, et al(杨 锐, 何水样, 武望婷,等). Acta Chimica Sinica(化学学报), 2004, 62(20): 2040. [18] ZHANG Rui-hua, LIU Jing-xin, SUN Yuan-hong(张瑞华, 刘景心,孙元洪). Chinese Journal of Rare Earths(稀土), 2005, 26(6): 83. [19] LI Xia(李 夏). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2004, 24(1): 92. [20] ZHAO Tian-zeng(赵天增). 1H Nuclear Magnetic Resonance Spectra(核磁共振氢谱). Beijing:Peking University Press(北京:北京大学出版社), 1983. 120. |
[1] |
LI Zhi1, WANG Xia1*, XU Can1*, LI Peng2, HUO Yu-rong1, FU Jing-yu1, WANG Pei1, FENG Fei3. Review of Spectral Characterization and Identification of Unresolved Space Objects[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2023, 43(05): 1329-1339. |
[2] |
SHAO Ke-man, FU Gui-yu, CHEN Su-yan, HONG Cheng-yi, LIN Zheng-zhong*, HUANG Zhi-yong*. Preparation of Molecularly Imprinted Fluorescent Probe for Rare Earth Complex and Determination of Malachite Green Residue[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(03): 808-813. |
[3] |
LI Zhi-yuan1, LIU Xue-lian1,2, ZHENG An-dong1, WANG Guo-dong1, XIA Guo1,3, LU Hong-bo1,2*. Research on the Spectral Analysis and Stability of Ultraviolet-Enhanced Thin Films with Stable and Tunable Graphene Oxide-Rare Earth Complexes[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2020, 40(02): 379-384. |
[4] |
SONG Si-yue, LIU Xu-wei, LIN Hong-xiao, WANG Xue-jin*,HE Zhi-wei. Spectral Characterization of Electrodeposited Cu2ZnSnS4 Thin Films on Fluorine-Doped Tin Oxide[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2019, 39(09): 2940-2945. |
[5] |
XIAO Xue-feng1, SUN Yong-jun1, 2*, SHEN Hao1, SUN Wen-qaun1, ZHENG Huai-li3, XU Yan-hua2, ZHU Cheng-yu1. Spectral Characterizations of CSC-P(AM-AA) with Function of Trapping Heavy Metals and Its Removal Efficiency of Cu2+[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2018, 38(06): 1809-1813. |
[6] |
JIANG Zhong-min1, KONG Ling-jun2, NIE Peng1, YU Hai-qi1. Study on the Spectral Characterization Model of Multi-Color Printer Based on LabPQR Dimension Reduction[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2018, 38(06): 1975-1981. |
[7] |
SUN Yong-jun1, 2, ZHENG Huai-li3, ZHAO Chun3, XIAO Xue-feng1, XU Yan-hua2, WU Hui-fang1, SUN Wen-quan1, REN Meng-jiao1, ZHU Cheng-yu1. The Spectral Characterizations of Chitosan Based Flocculants Synthesized by Photopolymerization[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2017, 37(08): 2527-2532. |
[8] |
LI Rui, FAN Ting-ting, QU Xiang-long, DONG Gao-yun, LI Jia-jia, LI Xia*, SONG Yu-xin, ZHAO Xin-meng, LI Xiang . Fluorescence Properties and the Detection of Nitrobenzene of Lanthanides Complex with 3,4-Thiophenedicarboxylic Acid and 1,10 Phenanthroline[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2016, 36(08): 2522-2526. |
[9] |
DONG Gao-yun, MA Xue, LI Jia-jia, LI Xia* . Lanthanum Coordination Polymer Based on Benzimidazole-Dicarboxylic Acid and Phenanthroline: Crystal Structure, Fluorescence and Fluorescent Sensing for Organic Small Molecules[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2015, 35(08): 2208-2211. |
[10] |
WANG Xiao-nan, YU Pei-zhi* . Synthesis and Characterization of PAM Derivative Weak Gel [J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2015, 35(03): 730-733. |
[11] |
SONG Yu-min, YANG Mei-ling,MA Jun-huai, ZHANG Yu-mei . Photochromic Properties of Complexes of Curcumin Aniline Schiff Base with Rare Earth [J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2013, 33(12): 3202-3206. |
[12] |
ZHANG Xin1, ZHU Chang-ming2, LUO Jian-cheng1, LI Wan-qing3, YANG Ji-wei3 . A Method for Water Body Adaptive Extraction from Remote Sensing Imagery Based on Local End Member Spectral Characterization[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2013, 33(06): 1670-1677. |
[13] |
XIA Jia-wei, ZHANG Yue, LU Lei, HAN Qiao-feng*. Preparation, Characterization and Photocatalysis of Bi2WO6 Nanocrystals[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2013, 33(05): 1304-1308. |
[14] |
TAO Dong-liang1,2,3, LI Hui-zhen4, CUI Yu-min1,3, JIA Ya-li4, LIU Shao-xuan2, XU Yi-zhuang2*, WANG Yong-zhong1, CHEN Ji-tang1, SHI Rui-juan1,3, ZHANG Wen-bao1, QIAO Xue-ling1, SUN Wen-zhong1, ZHANG Hong1 . Study on Preparations and Fluorescent Properties of Rare Earth Complex with Property of Fluorescence Sensor [J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2012, 32(09): 2473-2476. |
[15] |
JIANG Yu-xiang1, PANG Dao-lin1, HE Qiang2, LAI Cheng-yue1, ZHENG Huai-li2, LI Fang1* . Spectroscopy Study on the Selectively Distinguishing Cefalexin with the Molecular Imprinted Polymer [J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2011, 31(07): 1852-1856. |
|
|
|
|