Fluorescence modulation via isomer-dependent energy transfer in an azobenzene-functionalized poly(phenylenevinylene) derivative

Journal of Physical Chemistry B

Volumn 108, Issue 49, 2004, Pages 18789-18792

  Harbron, Elizabeth J ^a   Vicente, Diego A ^a   Hoyt, Mirth T ^a  

^a Asian and Middle Eastern Studies Program   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION SPECTRUM; AZOBENZENES; FLUORESCENCE MODULATION; PHOTOSTATIONARY STATE (PSS);

DERIVATIVES; ENERGY TRANSFER; FLUORESCENCE; ISOMERIZATION; ISOMERS; LIGHT MODULATION; ORGANIC POLYMERS; QUENCHING; ULTRAVIOLET RADIATION;

BENZENE;

EID: 10844228985     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp045651m     Document Type: Article

References (32)

1. Hide, F.; Diaz-Garcia, M. A.; Schwartz, B. J.; Heeger, A. J. Acc. Chem. Res. 1997, 30, 430.
2. Friend, R. H.; Gymer, R. W.; Holmes, A. B.; Burroughes, J. H.; Marks, R. N.; Taliani, C.; Bradley, D. D. C.; Santos, D. A. D.; Brédas, J. L.; Lögdlund, M.; Salaneck, W. R. Nature 1999, 397, 121.
3. Matsui, T.; Nagata, T.; Ozaki, M.; Fujii, A.; Onoda, M.; Teraguchi, M.; Masuda, T.; Yoshino, K. Synth. Met. 2001, 119, 599.
4. Yoshino, K.; Nagata, T.; Nakayama, K.; Fujii, A.; Ozaki, M.; Onoda, M. Mol. Mater. 2000, 12, 143.
5. A structurally similar polymer was synthesized by Wang and co-workers: Wang, G.; Li, M.; Yu, M.; Guo, C.; Chen, X.; Li, G.; Zhou, E. Liq. Cryst. 2000, 27, 867.
6. Wang, G.; Li, M.; Chen, X.; Wu, F.; Tian, W.; Shen, J. Macromol. Rapid Commun. 1999, 20, 591.
7. Myles, A. J.; Gorodetsky, B.; Branda, N. R. Adv. Mater. 2004, 16, 922.
8. Gorodetsky, B.; Sud, D.; Norsten, T. B.; Myles, A. J.; Branda, N. R. J. Porphyrins Phthalocyanines 2003, 7, 313.
9. Guo, X.; Zhang, D.; Zhou, Y.; Zhu, D. J. Org. Chem. 2003, 68, 5681.
10. Frigoli, M.; Mehl, G. H. Chem. Commun. 2004, 818.
11. Jin, M.; Lu, R.; Bao, C. Y.; Xu, T. H.; Zhao, Y. Y. Opt. Mater. 2004, 26, 85.
12. Irie, M.; Fukaminato, T.; Sasaki, T.; Tamai, N.; Kawai, T. Nature 2002, 420, 759.
13. Giordano, L.; Jovin, T. M.; Irie, M.; Jares-Erijman, E. A. J. Am. Chem. Soc. 2002, 124, 7481.
14. Song, L.; Jares-Erijman, E. A.; Jovin, T. M. J. Photochem. Photobiol. A: Chem. 2002, 150, 177.
15. Ceroni, P.; Laghi, I.; Maestri, M.; Balzani, V.; Gestermann, S.; Gorka, M.; Vögue, F. New J. Chem. 2002, 26, 66.
16. Asakawa, M.; Ashton, P. R.; Balzani, V.; Brown, C. L.; Credi, A.; Matthews, O. A.; Newton, S. P.; Raymo, F. M.; Shipway, A. N.; Spencer, N.; Quick, A.; Stoddart, J. F.; White, A. J. P.; Williams, D. J. Chem. Eur. J. 1999, 5, 860.
17. Bahr, J. L.; Kodis, G.; de la Garza, L.; Lin, S.; Moore, A. L; Moore, T. A.; Gust, D. J. Am. Chem. Soc. 2001, 123, 7124.
18. Norsten, T. B.; Branda, N. R. J. Am. Chem. Soc. 2001, 123, 1784.
19. Osuka, A.; Fujikane, D.; Shinmori, H.; Kobatake, S.; Irie, M. J. Org. Chem. 2001, 66, 3913.
20. Kawaia, T.; Sasakia, T.; Irie, M. Chem. Commun. 2001, 711.
21. Fern, V.; Scoponi, M.; Bignozzi, C. A.; Tyson, D. S.; Castellano, F. N.; Doyle, H.; Redmond, G. Nano Lett. 2004, 4, 835.
22. -1, data not shown).
23. The fluorescence kinetics are clearly faster than those measured by absorption during UV irradiation. Energy transfer to the trans azobenzene contributes to the observed fluorescence kinetics but not to absorption because the energy transfer alters the emission intensity but not the trans azobenzene population, which is monitored in the absorbance experiment. A more quantitative exploration of the kinetics is underway.
24. All experiments were conducted in dilute solution with absorbance less than 0.1 to minimize absorption of fluorometer excitation or polymer emission by the azobenzene side chains. Additionally, the observed fluorescence modulation effects were found to be independent of cuvette path length, a result that would not be expected if inner filter effects were operating. Poly(5-(decyloxy)-2- methoxy-1,4-phenylenevinylene) (DM-10-PPV), a control polymer without the azobenzene in the side chain, was mixed with decyloxyazobenzene in THF in proportions that simulated the MPA-10-PPV absorption spectrum. This control sample was submitted to the same irradiation conditions as for MPA-10-PPV; upon UV irradiation, the free decyloxyazobenzene underwent trans to cis isomerization and the polymer emission did not decrease (data not shown). Collectively, these controls demonstrate that the observed modulation is not due to inner filter effects or radiative energy transfer.
25. Vögtle, F. G.; Marius; Hesse, R.; Ceroni, P.; Maestri, M.; Balzani, V. Photochem. Photobiol Sci. 2002, 1, 45.
26. The direct cis to trans back-isomerization under UV irradiation makes only a minor contribution to the observed kinetics. This discussion also excludes the contribution of the thermal cis to trans back-isomerization, which is slow at room temperature (see Note 22).
27. max at time t by the absorbance in the dark, when the sample is roughly assumed to be 100% trans.
28. Lakowicz, J. R. Principles of Fluorescence Spectroscopy; Kluwer Academic/Plenum: New York, 1999; p 370.
29. Yip, W.-T.; Hu, D.; Vanden Bout, D. A.; Barbara, P. F. J. Phys. Chem. A 1998, 102, 7564.
30. Hu, D.; Yu, J.; Barbara, P. F. J. Am. Chem. Soc. 1999, 121, 6936.
31. Huser, T.; Yan, M.; Rothberg, L. J. Proc. Natl. Acad. Sci. 2000, 97, 11187.
32. 0, so the energy transfer efficiency to the cis isomer was not calculated by eq 2. However, it would be higher than to the trans isomer due to the increased value of the overlap integral for the cis versus the trans azobenzene.