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2012 , Vol. 70 >Issue 9: 1081 - 1087

DOI: https://doi.org/10.6023/A1112121

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
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  • 东南大学化学化工学院 南京 211189

收稿日期: 2011-12-12

  修回日期: 2012-02-08

  网络出版日期: 2012-05-18

基金资助

国家自然科学基金(No. 21075015)资助项目.

收起

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

  • TANG Lan-Lan ,
  • QI Zheng-Jian ,
  • HONG Man-Xin ,
  • LI Nan ,
  • SHEN Wei ,
  • YANG Fan ,
  • JI Xin ,
  • HU Ai-Jiang
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  • School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189

Received date: 2011-12-12

  Revised date: 2012-02-08

  Online published: 2012-05-18

Supported by

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

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摘要

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

本文引用格式

唐兰兰 , 祁争健 , 洪满心 , 李楠 , 沈伟 , 杨帆 , 吉昕 , 胡爱江 . 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[J]. 化学学报, 2012 , 70(9) : 1081 -1087 . DOI: 10.6023/A1112121

Abstract

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

参考文献

1 Preininger, C.; Klimant, I.; Wolfbeis, O. S. Anal. Chem.1994, 66, 1841.  

2 Huynh, L.; Wang, Z.; Yang, J.; Stoeva, V.; Lough, A.; Manners, I.; Winnik, M. A. Chem. Mater. 2005, 17, 4765.  

3 Bukowski, R. M.; Ciriminna, R.; Pagliaro, M.; Bright, F. V. Anal. Chem. 2005, 77(8), 2670.

4 Tang, Y.; Tehan, E. C.; Tao, Z.; Bright, F. V. Anal. Chem.2003, 75, 2407.  

5 McEvoy, A. K.; McDonagh, C. M.; MacCraith, B. D. Analyst1996, 121, 785.  

6 Dimarco, G.; Lanza, M.; Pieruccini, M.; Campagna, S. Adv. Mater. 1996, 8, 576.  

7 Dimarco, G.; Lanza, M.; Campagna, S. Adv. Mater. 1995, 7,468.  

8 Ma, Y. G.; Cheung, T. C.; Che, C. M.; Shen, J. C. Thin Solid Films 1998, 333(1-2), 225.  

9 Leiner, M. J. P. Anal. Chim. Acta 1991, 255, 210.

10 Lübbers, D. W.; Opitz, N. Sens. Actuators, B 1983, 4, 642.

11 Sharma, A.; Wolfbeis, O. S. Anal. Chim. Acta 1988, 212,261.  

12 Wolfbeis, O. S.; Posch, H. E.; Kroneis, H. W. Anal. Chem.1985, 57, 2556.  

13 DeRosa, M. C.; Mosher, P. J.; Glenn, P. A. Y.; Focsaneanu, K.-S.; Crutchley, R. J.; Christopher, E. B. E. Inorg. Chem.2003, 42(16), 4864.  

14 Kimura, F.; Rodriguez, M.; McCann, J.; Carlson, B.; Dabiri, D.; Gamal, E. K.; James, B. C.; Xia, Y. N.; Gouterman, M. Rev. Sci. Instrum. 2008, 79(7), 074102.  

15 DeRosa, M. C.; Hodgson, D. J.; Enright, G. D.; Dawson, B.; Evans, C. E. B.; Crutchley, R. J. J. Am. Chem. Soc. 2004,126, 7619.  

16 Fischer, L. H.; Stich, M. I. J.; Wolfbeis, O. S.; Tian, N.; Holder E.; Sch?ferling, M. Chem. Eur. J. 2009, 15, 10857  

17 Tyson, D. S.; Bialecki, J.; Castellano, F. N. Chem. Commun.2000, (23), 2355.

18 Singer, E.; Duveneck, G. L.; Ehrat, M.; Widmer, M. Sens. Actuators, A 1994, 41/42, 542.  

19 Xu, W.; MacDonough, R. C.; Langsdorf, B.; Demas, J. N.; DeGraff, B. A. Anal. Chem. 1994, 66, 4133.  

20 Chuang, H.; Arnold, M. A. Anal. Chim. Acta 1998, 368, 83.  

21 Sacksteder, L.; Demas, J. N.; DeGraff, B. A. Anal. Chem.1993, 65(23), 3480.

22 Hartmann, P.; Leiner, M. J. P.; Lippitsch, M. E. Anal. Chem. 1995, 67(1), 88.

23 Klimant, I.; Wolfbeis, O. S. Anal. Chem. 1995, 67, 3160.  

24 Lee, S.-K.; Okura, I. Anal. Sci. 1997, 13(4), 535.

25 Bacon, J. R.; Demas, J. N. Anal. Chem. 1987, 59, 2781.

26 Carraway, E. R.; Demas, J. N.; DeGraff, B. A.; Bacon, J. R. Anal. Chem. 1991, 63, 337.  

27 Brian, D. M.; Colette, M. M.; Gerard, O. Analyst 1993,118(4), 385.

28 Lv, T. P. Chem. Sens. 1997, 17(4), 279 (in Chinese). (吕太平, 化学传感器, 1997, 17(4), 279.)  

29 Lu, X.; Winnik, M. A. Chem. Mater. 2001, 13, 3449.  

30 Lei, B. F.; Li, B.; Zhang, H. R.; Lu, S. Z.; Zheng, Z. H.; Li, W. L.; Wang, Y. Adv. Funct. Mater. 2006, 16, 1883.  

31 Zhang, H. R.; Li, B.; Lei, B. F.; Li, W. L. J. Lumin. 2008,128, 1331.  

32 Wu, X. D.; Song, L. T.; Li, B.; Liu, Y. H. J. Lumin. 2010,130, 374.  

33 Lupo, F.; Fragalà, M. E.; Gupta, T.; Mamo, A.; Aureliano, A.; Bettinelli, M.; Speghini, A.; Gulino, A. J. Phys. Chem. C 2010, 114, 13459.

34 Lei, B. F.; Li, B.; Zhang, H. R.; Zhang, L. M.; Li, W. L. J. Phys. Chem. C 2007, 111, 11291.  

35 Wang, S. L.; Li, B.; Zhang, L. M.; Liu, L. N.; Wang, Y. H. Appl. Organomet. Chem. 2011, 25, 21.  

36 Chiabrera, A.; Zitti, E. D.; Costa, F.; Bisio, G. M. J. Phys. D: Appl. Phys. 1989, 22, 1573.

37 Sprintschnik, G.; Sprintschnik, H. W.; Kirsch, P. P.; Whitten, D. G. J. Am. Chem. Soc. 1977, 99(15), 4949.

38 Wu, X. D.; Cong, Y.; Liu, Y. D.; Ying, J.; Li, B. J. Sol-Gel Sci. Technol. 2009, 49, 356.

39 Lin, W. H.; Sun, W. L.; Sun, Q. H.; Yang, J.; Shen, Z. Q. J. Phys. Chem. C 2009, 113(39), 16885.  

40 Santos, C. M. G.; Gunnlaugsson, T. Supramol. Chem. 2009,21(1-2), 174.  

41 Loewe, R. S.; Khersonsky, S. M.; McCullough, R. D. Adv. Mater. 1999, 11, 250.  

42 Antonin, C.; Bohumil, Z. CS 226921[z4], 1986 [Chem. Abstr. 1986, 106, 50180].

43 Sprouse, S.; King, K. A.; Spellane, P. J.; Watts, R. J. J. Am. Chem. Soc. 1984, 106, 6649.

44 Lamansky, S.; Djurovich, P.; Murphy, D.; Abdel-Razzaq, F.; Kwong, R.; Tsyba, I.; Bortz, M.; Mui, B.; Bau, R.; Thompson, M. E. Inorg. Chem. 2001, 40, 1707.

45 Demas, J. N.; Crosby, G. A. J. Phys. Chem. 1971, 75(8),991.

46 Malins, C.; Fanni, S.; Glever, H. G.; Vos, J. G.; MacCraith, B. D. Anal. Commun. 1999, 36, 3.  

47 Gouterman, M. J. Chem. Educ. 1997, 74(6), 699.

48 Demas, J. N.; DeGraff, B. A.; Xu, W. Y. Anal. Chem. 1995,67(8), 1377.
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