物理化学学报 >> 2013, Vol. 29 >> Issue (07): 1408-1414.doi: 10.3866/PKU.WHXB201305081

热力学,动力学和结构化学 上一篇    下一篇

苯并咪唑衍生配体锌-铕(或铽)异金属双核配合物的合成、结构与光学性质

赵顺省1, 张召2, 石国香2, 冯维旭2, 吕兴强2, 刘向荣1   

  1. 1 西安科技大学化学与化工学院, 西安 710054;
    2 西北大学, 陕西省物理无机化学重点实验室, 西安 710069
  • 收稿日期:2013-02-04 修回日期:2013-05-08 发布日期:2013-06-14
  • 通讯作者: 赵顺省, 吕兴强 E-mail:shshzhao@xust.edu.cn;lvxq@nwu.edu.cn
  • 基金资助:

    国家自然科学基金(21103135, 21173165, 21073139);陕西省自然科学基础研究计划(2011JQ2011);陕西省教育厅自然科学专项(12JK0622)和西安科技大学博士启动金(2010QDJ030)资助项目

Heterobinuclear Zn-Eu or Zn-Tb Complexes Formed from Benzimidazole Derivatives and Metal Salts: Synthesis, Structures and Photophysical Properties

ZHAO Shun-Sheng1, ZHANG Zhao2, SHI Guo-Xiang2, FENG Wei-Xu2, LÜ Xing-Qiang2, LIU Xiang-Rong1   

  1. 1 College of Chemistry and Chemical Engineering, Xi’an University of Science & Technology, Xi’an 710054, P. R. China;
    2 Shaanxi Key Laboratory of Physico-inorganic Chemistry, Northwest University, Xi’an 710069, Shaanxi, P. R. China
  • Received:2013-02-04 Revised:2013-05-08 Published:2013-06-14
  • Contact: ZHAO Shun-Sheng, Lü Xing-Qiang E-mail:shshzhao@xust.edu.cn;lvxq@nwu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21103135, 21173165, 21073139), Natural Science Basic Research Plan in Shaanxi Province of China (2011JQ2011), Scientific Research Program Funded by Shaanxi Provincial Education Commission, China (12JK0622), and Foundation of Xi'an University of Science and Technology, China (2010QDJ030)

摘要:

合成了四个锌-铕(或铽)异金属双核配合物[ZnLnL1(NO3)3Py] (Ln=Eu (1), Tb (2); HL1=1-H-2-(2-羟基-3-甲氧基苯基)苯并咪唑; Py=吡啶)和[ZnLnL2(NO3)3Py] (Ln=Eu (3), Tb (4); HL2=1-H-2-(2-羟基-3-甲氧基-5-溴苯基)苯并咪唑; Py=吡啶), 其中123是单晶态, 化合物4则为多晶样品; 通过单晶X射线衍射、元素分析、傅里叶变换红外光谱和电喷雾质谱对化合物进行了表征. 化合物的紫外-可见吸收光谱、荧光激发和发射光谱表明配体的激发态能量有效传递到配合物中的镧系金属离子中, 含有铽(III)离子的配合物发射出其特征发射光谱, 而含有铕(III)离子的配合物由于其它去活方式, 没有辐射出铕(III)离子的特征发射光谱.

关键词: 苯并咪唑衍生配体, 敏化作用, 能量传递, 天线效应, 特征发射光谱

Abstract:

Four isostructural heterobinuclear Zn-Ln (Ln=Eu or Tb) complexes are prepared through the self-assembly of benzimidazole derivatives 2-(2-hydroxy-3-methoxyphenyl)benzimidazole (HL1) or 2-(5-bromo-2-hydroxy-3-methoxyphenyl)benzimidazole (HL2) with Zn(CH3COO)2·2H2O and Eu(NO3)3·6H2O or Tb(NO3)3·6H2O). The complexes are characterized by single-crystal X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, elementary analysis, and electrospray ionization mass spectrometry (ESIMS). Three of the complexes form single crystals, while the fourth is polycrystalline. UV-Vis absorption, excitation and emission spectra of the Tb3+-based complexes reveal strong, characteristic luminescence from Tb3+ with emissive lifetimes in the microsecond range. Therefore, Tb3+ has been sensitized from the excited state of the ligands because of effective intramolecular energy transfer. The Eu3+ complexes do not show characteristic emission because of deactivation by a different pathway.

Key words: Benzimidazole derivative, Sensitization, Energy transfer, Antennae effect, Characteristic emission

MSC2000: 

  • O641