Linear free-energy relationship for electron-transfer processes of pyrrolidinofullerenes with tetrakis(dimethylamino)ethylene in ground and excited states

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Chuping Luo, Mamoru Fujitsuka, Chun-Hui Huang and Osamu Ito


Abstract

Systematic studies of electron-transfer processes in the ground states and excited triplet states of pyrrolidinofullerenes {C60(C3H6N)R [R=H (1), p-C6H4NO2 (2), p-C6H4CHO (3), p-C6H5 (4), p-C6H4OMe (5), p-C6H4NMe2 (6)]} with tetrakis(dimethylamino)ethylene (TDAE) have been carried out by steady-state and transient absorption measurements in the visible–NIR region. Analyses of the equilibria of the electron-transfer processes in the ground states indicate that free ion radicals are produced in polar solvents. Photoinduced electron-transfer processes viaT(C60(C3H6N)R)* were observed by applying a perturbation to the equilibria of the electron-transfer reactions in the ground states by laser flash photolysis. Based on the relationship of the thermodynamic data and kinetic data, the electron-transfer rate constants in the ground states (ketG) can be evaluated. The ketG values are affected by the substituents to a smaller extent compared with the equilibrium constants (K) in polar solvents; α=0.6 in Δ log ketG=α Δ log K. This α value indicates that the activation energies of forward electron transfer in the ground states vary moderately with the thermodynamic stabilities of (C60(C3H6N)R)-. Electron-transfer rate constants viaT(C60(C3H6N)R)*, which are close to the diffusion-controlled limit, do not show a large substituent effect (α′=0), because of their highly exothermic processes. Such a linear free-energy relationship can be extended to other systems such as T(C60(C3H6N)R)*/N,N-dimethylaniline, from which valuable information for electron-transfer processes can be obtained.


References

  1. (a) T. Suzuki, Q. Li, K. C. Khemani, F. Wudl and Ö Almarsson, Science, 1991, 254, 1186 CAS; (b) F. Wudl, Acc. Chem. Res., 1992, 25, 157 CrossRef CAS; (c) A. Hirsch, A. Soi and H. R. Karfunkel, Angew. Chem., Int. Ed. Engl., 1992, 31, 766 CrossRef; (d) C. Bingel, Chem. Res., 1993, 126, 1957 Search PubMed; (e) J. M. Hawkins, M. Nambu and A. Meyer, J. Am. Chem. Soc., 1994, 116, 7642 CrossRef CAS; (f) S. R. Wilson, Q. Lu, J. Cao, Y. Wu, C. J. Welch and D. I. Schuster, Tetrahedron, 1996, 52, 5131 CrossRef CAS; (g) J.-N. Nierengarten, T. Habicher, R. Kessinger, F. Cardullo and F. Diederich, Helv. Chim. Acta, 1997, 80, 2238 CrossRef CAS; (h) K. M. Kadish, X. Gao, E. V. Caemelbecke, T. Hirasaka, T. Suenobu and S. Fukuzumi, J. Phys. Chem. A, 1998, 102, 3898 CrossRef CAS.
  2. (a) Y. Wang, Nature, 1992, 356, 585 CrossRef CAS; (b) K. C. Hwang and D. Mauzerall, J. Am. Chem. Soc., 1992, 114, 9705 CrossRef CAS; (c) K. C. Hwang and D. Mauzerall, Nature, 1993, 361, 138 CrossRef CAS; (d) Y. Wang, R. West and C.-H. Yuan, J. Am. Chem. Soc., 1993, 115, 3844 CrossRef CAS; (e) C. P. Luo, C. H. Huang, L. B. Gan, D. J. Zhou, W. S. Xia, Q. K. Zhuang, Y. Zhao and Y. Y. Huang, J. Phys. Chem., 1996, 100, 16685 CrossRef CAS.
  3. (a) R. C. Haddon, Nature, 1991, 350, 320 CrossRef CAS; (b) A. F. Hebard, M. J. Rosseinsky, R. C. Haddon, D. W. Murphy, S. H. Glarum, T. T. M. Palstra, A. P. Ramirez and A. R. Kortan, Nature, 1991, 350, 600 CrossRef CAS; (c) K. Tanigaki, T. W. Ebbesen, J. Sato, J. Mizuki, J. S. Tsai, Y. Kubo and S. Kuroshima, Nature, 1991, 352, 222 CrossRef CAS; (d) P. J. Benning, D. M. Poirier, T. R. Ohno, Y. Chen, M. B. Jost, F. Stepniak, G. H. Kroll, J. H. Weaver, J. Fure and R. E. Smalley, Phys. Rev. B, 1992, 45, 6899 CrossRef CAS.
  4. (a) P.-K. Allemand, K. C. Khemani, A. Koch, F. Eudl, K. Holczer, S. Donovan, G. Gruner and J. D. Thompson, Science, 1991, 253, 301 CrossRef CAS; (b) K. Tanaka, A. A. Zakhidov, K. Yoshizawa, K. Okahara, T. Yamabe, K. Yasuki, K. Kikuchi, S. Sizuki, I. Ikemoto and Y. Achiba, Phys. Lett. A, 1992, 164, 354 CrossRef CAS; (c) V. Buntar, F. M. Sauerzopf and H. W. Weber, Aust. J. Phys., 1997, 50, 329 Search PubMed; (d) S. Hino, K. Umishima, K. Iwasaki, K. Tanaka, T. Sato, T. Yamabe, K. Yoshizawa and K. Okahara, J. Phys. Chem. A, 1997, 101, 4346 CrossRef CAS.
  5. (a) S. H. Friedman, D. L. DeCamp, R. P. Sijbesma, G. Srdanov, F. Wudl and G. L. Kenyon, J. Am. Chem. Soc., 1993, 115, 6506 CrossRef CAS; (b) R. Sijbesma, G. Srdanov, F. Wudl, J. A. Castoro, C. Wilkins, S. H. Friedman, D. L. De Camp and G. L. Kenyon, J. Am. Chem Soc., 1993, 115, 6510 CrossRef CAS; (c) A. S. Boutorine, H. Tokuyama, M. Takasugi, H. Isobe, N. Nakamura and C. Helene, Angew. Chem., 1994, 23, 2526; (d) A. Hirsch, The Chemistry of the Fullerenes, Thieme Medical Publishers Inc., New York, 1994 Search PubMed.
  6. (a) M. Prato, T. Suzuki, F. Wudl, V. Lucchini and M. Maggini, J. Am. Chem. Soc., 1993, 115, 7876 CrossRef CAS; (b) M. S. Meier, M. Poplawska and A. L. Compton, J. Am. Chem. Soc., 1994, 116, 7044 CrossRef CAS; (c) T. Suzuki, Y. Maruyama, T. Akasaka, W. Ando, K. Kobayashi and S. Nagase, J. Am. Chem. Soc., 1994, 116, 1359 CrossRef CAS; (d) N. Martin, L. Sanchez, B. Illescas and I. Perez, Chem. Rev., 1998, 98, 2527 CrossRef CAS.
  7. (a) R. M. Williams, J. M. Zwier and J. W. Verhoeven, J. Am. Chem. Soc., 1995, 117, 4093 CrossRef CAS; (b) K. G. Thomas, V. Biju, M. V. George, D. M. Guldi and P. V. Kamat, J. Phys. Chem. A, 1998, 102, 5341 CrossRef CAS.
  8. D. M. Guldi, M. Maggini, G. Scorrano and M. Prato, J. Am. Chem. Soc., 1997, 119, 974 CrossRef CAS.
  9. (a) D. Kuciavskas, S. Lin, G. R. Seely, A. L. Moore, T. A. Moore, D. Gust, T. Drovetskaya, C. A. Reed and P. D. W. Boyd, J. Phys. Chem., 1996, 100, 1592; (b) H. Imahori, K. Hagiwara, M. Aoki, T. Akiyama, S. Taniguchi, T. Okada, M. Shirakawa and Y. Sakata, J. Am. Chem. Soc., 1996, 118, 11771 CrossRef CAS.
  10. (a) P. A. Liddell, D. Kuciauskas, J. P. Sumida, B. Nash, D. Nguyen, A. L. Moore, T. A. Moore and D. Gust, J. Am. Chem. Soc., 1997, 119, 1400 CrossRef CAS; (b) H. Imahori, S. Cardoso, D. Tatman, S. Lin, L. Noss, G. R. Seely, L. Sereno, J. Chessa de Silber, T. A. Moore, A. L. Moore and D. Gust, Photochem. Photobiol., 1995, 62, 1009.
  11. (a) D. M. Guldi, H. Hungerühler and K.-D. Asmus, J. Phys. Chem., 1995, 99, 13487 CrossRef CAS; (b) B. Ma, E. C. Bunker, R. Guduru, X. Zhang and Y.-P. Sun, J. Phys. Chem. A, 1997, 101, 5626 CrossRef CAS; (c) D. K. Palit, H. Mohan, P. R. Birkett and J. P. Mittal, J. Phys. Chem. A, 1997, 101, 5418 CrossRef CAS; (d) C. Luo, M. Fujitsuka, C.-H. Huang and O. Ito, J. Phys. Chem. A, 1998, 102, 8716 CrossRef CAS.
  12. (a) D. M. Guldi, H. Hungerühler and K.-D. Asmus, J. Phys. Chem., 1995, 99, 9380 CrossRef CAS; (b) D. M. Guldi and K.-D. Asmus, J. Phys. Chem. A, 1997, 101, 1472 CrossRef CAS.
  13. (a) N. Wiberg, Angew. Chem., Int. Ed. Engl., 1968, 7, 766 CrossRef CAS; (b) K. Kuwata and D. Geske, J. Am. Chem. Soc., 1964, 86, 2101 CrossRef CAS.
  14. M. Fujitsuka, C. Luo and O. Ito, J. Phys. Chem. B, 1999, 103, 445 CrossRef CAS.
  15. A. Watanabe and O. Ito, J. Phys. Chem., 1994, 98, 7736 CrossRef CAS.
  16. (a) G. A. Heath, J. E. McGrady and R. L. Martin, J. Chem. Soc., Chem. Commun., 1992, 1272 RSC; (b) R. D. Bolskar, S. H. Gallagher, R. S. Armstrong, P. A. Lay and C. A. Reed, Chem. Phys. Lett., 1995, 247, 57 CrossRef CAS.
  17. P. C. Trulove, R. T. Carlin, G. R. Eaton and S. S. Eaton, in Fullerene, ed. R. S. Ruoff and K. M. Kadish, Electrochemical Society, Pennington, NJ, 1995, p. 362 Search PubMed.
  18. C. Luo, M. Fujitsuka, A. Watanabe, O. Ito, L. Gan, Y. Huang and C.-H. Huang, J. Chem. Soc., Faraday Trans., 1998, 94, 527 RSC.
  19. H. A. Benesi and H. A. Hildebrand, J. Am. Chem. Soc., 1949, 71, 2703 CrossRef CAS.
  20. (a) P. Scharff and N. Feldtner, Mol. Phys. Rep., 1997, 18/19, 137 Search PubMed; (b) V. Brezova, A. Stasko, P. Rapta, D. M. Guldi, K.-D. Asmus and K.-P. Dinse, Magn. Reson. Chem., 1997, 35, 795 CrossRef CAS.
  21. P. R. Wells, Linear Free Energy Relationship, Academic Press Inc., New York, 1968 Search PubMed.
  22. D. Rehm and A. Weller, Isr. J. Chem., 1970, 8, 259 CAS.
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