化学学报 ›› 2012, Vol. 70 ›› Issue (09): 1081-1087.DOI: 10.6023/A1112121 上一篇    下一篇

研究论文

具不同官能团钌(II)邻菲啰啉配合物氧淬灭性能的比较研究

唐兰兰, 祁争健, 洪满心, 李楠, 沈伟, 杨帆, 吉昕, 胡爱江   

  1. 东南大学化学化工学院 南京 211189
  • 投稿日期:2011-12-12 修回日期:2012-02-08 发布日期:2012-05-18
  • 通讯作者: 祁争健 E-mail:qizhengjian@seu.edu.cn
  • 基金资助:

    国家自然科学基金(No. 21075015)资助项目.

Comparison Study of Oxygen Quenching of Ru(II) Phenanthroline Complexes with Different Functional Groups

Tang Lanlan, Qi Zhengjian, Hong Manxin, Li Nan, Shen Wei, Yang Fan, Ji Xin, Hu Aijiang   

  1. School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189
  • Received:2011-12-12 Revised:2012-02-08 Published:2012-05-18
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21075015).

设计并制备具不同官能团的钌(II)邻菲啰啉配合物——[Ru(bpy)2(phen-NO2)](PF6)2 (1), [Ru(bpy)2(phen-Br)](PF6)2(2), [Ru(bpy)2(phen-NH2)](PF6)2 (3), [Ru(bpy)2(bphen)](PF6)2 (4), 其中, bpy 为2,2'-联吡啶, phen-NO2 为5-硝基-邻菲啰啉,phen-Br 为5-溴-1,10-菲啰啉, phen-NH2 为5-氨基-邻菲啰啉, bphen 为4,7-二苯基-邻菲啰啉. 借助核磁共振(NMR)、红外光谱(FTIR)、元素分析、紫外可见光谱(UV-vis)和荧光光谱法对其进行了分析与表征. 结果表明: 配合物2~4 在蓝-紫色可见光区域有较强吸收、可发射出明亮的橙红色荧光、具荧光量子效率(Φ)高、激发态寿命(τ)长、Stocks 位移值较大(147~180 nm)和优良的氧致荧光淬灭性能(Ksv≥3.5, (I0/I)max≥4.0)等光物理性质. 其中, 具接枝型官能团氨基的配合物3 的量子效率(Φ)=10%, τ=381.8 ns, Ksv=3.49, (I0/I)max=4.33; 而溴修饰的配合物2 以高达18%的荧光量子效率、634.7 ns 的激发态寿命、180 nm 的Stocks 位移和Ksv=4.59, 氧淬灭参数(I0/I)max=5.29, 使之最有希望成为接枝型、较高性能的光学氧传感器的候选氧敏指示剂.

关键词: 钌(II)配合物, 邻菲啰啉, 发光体, 氧淬灭, 氧传感器

Ruthenium(II) phenanthroline complexes with different functional groups: [Ru(bpy)2(phen- NO2)](PF6)2 (1), [Ru(bpy)2(phen-Br)](PF6)2 (2), [Ru(bpy)2(phen-NH2)](PF6)2 (3), [Ru(bpy)2(bphen)](PF6)2 (4) (where bpy=2,2'-bipyridyl, phen-NO2=5-nitro-phenanthroline, phen-Br=5-bromo-phenanthroline, phen-NH2=5-amino-phenanthroline, bphen=bathophenanthroline) were synthesized. They were characterized and analyzed by NMR, FTIR, elemental analysis and UV-Vis absorption and photoluminesence spectroscopy measurements, respectively. The investigations indicate that complexes 2~4 emit bright orange- red fluorescence and have intensely visible absorption in blue-purple region. Complexes 2~4 show the photophysics properties of high quantum efficiencies (Φ), long excited-state luminescence lifetime (τ), large Stocks shift (147~205 nm) and good oxygen-induced luminescence quenching properties (Ksv ≥3.5, (I0/I)max≥4.0). Among them, complex 3 grafted by an amino functional group has a Φ of 10%, a τ of 381.8 ns, a Ksv of 3.49 and the maximum I0/I factor of 4.33. However, complex 2 grafted by a bromine group shows higher Φ of 18%, longer luminescence τ of 635 ns, larger Ksv of 4.59 and the maximum I0/I factor up to 5.29. These properties make it a promising fluorescence indicator applied in grafting and high performance optics oxygen sensor.

Key words: Ru(II) complex, phenanthroline, luminophore, oxygen quenching, oxygen sensor