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Inter- and Intramolecular Quenching of Porphyrin Excited States by Quinones

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Supramolecular Photochemistry

Part of the book series: NATO ASI Series ((ASIC,volume 214))

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Abstract

We have measured the bimolecular rate constants for quenching of the excited singlet and triplet states of the free-base and zinc forms of tetraphenylporphine (TPP) by three quinones with greatly different reduction potentials in several solvents spanning a range of dielectric constant and viscosity. Where available, we have made comparisons with unimolecular rate data for some analogous linked systems. Our data indicate that the orientation of the donor and acceptor not only effects the rates of excited-state quenching, but can also determine whether such interactions result in net electron transfer. In bimolecular interactions, the geometry between the donor and acceptor is not restricted, and fluorescence quenching can be efficient even when net electron transfer is energetically unfavorable. However, in linked systems, when the geometries of the two π-ring systems are restricted, no fluorescence quenching is observed unless the energy requirements for net electron transfer are met. The rates of both inter- and intramolecular quenching of excited singlet states correlate with the energetics for electron transfer, but other mechanisms appear to be involved in intermolecular quenching of the triplet state of free-base TPP.

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References

  1. For a recent, comprehensive review see: Connolly, J.S.; Bolton, J.R. in Photoinduced Electron Transfer (Fox, M.A.; Chanon, M., eds.), Elsevier Science Publishers, Amsterdam, 1987 (to be published).

    Google Scholar 

  2. Connolly, J.S. in Photochemical Conversion and Storage of Solar Energy, 1982, (Rabani, J., ed.) Part A, Weizmann Science Press of Israel, Jerusalem, 1982, pp 175–204.

    Google Scholar 

  3. Connolly, J.S.; Turner, J.A in Photochemical Conversions, (Braun, A.M., ed.) Presses Polytechniques Romandes, Lausanne, Switzerland, 1983, pp 73–130, and references cited.

    Google Scholar 

  4. Seely, G.R. Photochem. Photobiol. 27, 639–654 (1978).

    Article  CAS  Google Scholar 

  5. Creed, D.; Caldwell, R.A. Photochem. Photobiol. 41, 715–739 (1985), and references cited.

    Article  CAS  Google Scholar 

  6. Harriman, A.; Porter, G.; Wilowska, A. J. Chem. Soc. Faraday Trans. 279, 807–816 (1983).

    Google Scholar 

  7. Gouterman, M.; Holten, D. Photochem. Photobiol. 25, 85–92 (1977).

    Article  CAS  Google Scholar 

  8. Holten, D. Ph.D. Thesis, University of Washington, Seattle, 1976.

    Google Scholar 

  9. Holten, D. Gouterman, M., Parson, W.W.; Windsor, M.W.; Rockley, M.G. Photochem. Photobiol. 23, 415–423 (1976).

    Article  CAS  Google Scholar 

  10. Fendler, J.H. J. Phys. Chem. 89, 2730–2740 (1985), and references cited.

    Article  CAS  Google Scholar 

  11. Hurst, J.K.; Thompson, D.H.P; Connolly, J.S. J. Am. Chem. Soc. 109, 507–515 (1987), and references cited.

    Article  CAS  Google Scholar 

  12. Miller, J.R.; Beitz, J. V.; Huddleston, R.K. J. Am. Chem. Soc. 106, 5057–5068 (1984).

    Article  CAS  Google Scholar 

  13. Marcus, R.A. J. Chem. Phys. 24, 966–978 (1956).

    Article  CAS  Google Scholar 

  14. Marcus, R.A. Ann. Rev. Phys. Chem. 15, 155–196 (1964).

    Article  CAS  Google Scholar 

  15. Marcus, R.A.; Sutin, N. Biochim. Biophys. Acta 811, 265–322 (1985).

    CAS  Google Scholar 

  16. Newton, M.D.; Sutin, N. Ann. Rev. Phys. Chem. 35, 437–480 (1984).

    Article  CAS  Google Scholar 

  17. Wasielewski, M.R.; Niemczyk, M.P.; Svec, W.A.; Pewitt, E.B. J. Am. Chem. Soc. 107, 1080–1082 (1985).

    Article  CAS  Google Scholar 

  18. Irvine, M.P.; Harrison, R.J.; Beddard, G.S.; Leighton, P.; Sanders, J.K.M. Chem. Phys. 104, 315–324 (1986).

    Article  CAS  Google Scholar 

  19. Miller, J.R.; Calcaterra, L.T.; Closs, G.L. J. Am. Chem. Soc. 106, 3047–3049 (1984).

    Article  CAS  Google Scholar 

  20. Deisenhofer, J.; Epp, O.; Miki, K.; Huber, R.; Michel, H. J. Mol. Biol. 180, 385–398 (1984); Nature 318, 618–624 (1985).

    Article  CAS  Google Scholar 

  21. Leland, B.A.; Joran, A.D.; Felker, P.M.; Hopfield, J.J.; Zewail, A.H.; Dervan, P.B. J. Phys. Chem. 89, 5571–5573 (1985).

    Article  CAS  Google Scholar 

  22. Schenck, C.C.; Blankenship, R.E.; Parson, W.W. Biochim. Biophys. Acta 680, 44–59 (1982).

    Article  CAS  Google Scholar 

  23. Den Blanken, H.J.; Hoff, A.J. Biochim. Biophys. Acta 681, 365–374 (1982).

    Article  Google Scholar 

  24. Barboy, N.; Feitleson, J. J. Phys. Chem. 88, 1065–1068 (1984).

    Article  CAS  Google Scholar 

  25. Roy, J.K.; Whitten, D.G. J. Am. Chem. Soc. 93, 7093–7094 (1971); ibid. 94, 7162–7164 (1972).

    Article  CAS  Google Scholar 

  26. Roy, J.K.; Carroll, F.A.; Whitten, D.G. J. Am. Chem. Soc. 96, 6349–6355 (1974).

    Article  CAS  Google Scholar 

  27. Harriman, A.; Porter, G.; Searle, N. J. Chem. Soc. Faraday Trans. II 75, 1515–1521 (1979).

    Article  CAS  Google Scholar 

  28. Wilford, J.H.; Archer, M.D.; Bolton, J.R.; Ho, T.-F.; Schmidt, J.A.; Weedon, A.C. J. Phys. Chem. 89, 5395–5398 (1985).

    Article  CAS  Google Scholar 

  29. Archer, M.D.; Gadzekpo, V.P.Y, (unpublished results).

    Google Scholar 

  30. Schmidt, J.A.; McIntosh, A.R.; Weedon, A.C.; Bolton, J.R.; Connolly, J.S.; Hurley, J.K.; Wasielewski, M.R. J. Am. Chem. Soc. (submitted).

    Google Scholar 

  31. Schmidt, J.A.; Siemiarczuk, A.; Weedon, A.C.; Bolton, J.R. J. Am. Chem. Soc. 107, 6112–6114 (1985).

    Article  CAS  Google Scholar 

  32. Schmidt, J.A. Ph.D. Thesis, The University of Western Ontario, London, Ontario, 1986.

    Google Scholar 

  33. Wasielewski, M.R.; Niemczyk, M.P. J. Am. Chem. Soc. 106, 5043–5045 (1984).

    Article  CAS  Google Scholar 

  34. Wasielewski, M.R.; Niemczyk, M.P. ACS Symp. Ser. 321, 154–165 (1986).

    Article  CAS  Google Scholar 

  35. Adler, A.D.; Longo, F.R.; Finarelli, J.D.; Goldmacher, J.; Assour, J.; Korsakoff, L. J. Org. Chem. 32, 476 (1967).

    Article  CAS  Google Scholar 

  36. In addition to TPP (5,10,15,20-tetraphenylporphine) and TTP (the tolyl analog), other abbreviations are: TTPa [5-(4-carboxyphenyl)-10,15,20-tri(p-tolyl)porphine] and TTPm (the corresponding methyl ester).

    Google Scholar 

  37. Hurley, J.K; Bell, W.L.; Marsh, K.L.; Wasielewski, M.R.; Connolly, J.S. (to be submitted).

    Google Scholar 

  38. Linschitz, H.; Sarkanen, K. J. Am. Chem. Soc. 80, 4826–4832 (1958).

    Article  CAS  Google Scholar 

  39. Pekkarinen, L.; Linschitz, H. J. Am. Chem. Soc. 82, 2407–2411 (1960).

    Article  CAS  Google Scholar 

  40. Linschitz, H.; Steel, C.; Bell, J.A. J. Phys. Chem. 66, 2574–2576 (1962).

    Article  CAS  Google Scholar 

  41. Connolly, J.S., Gorman, D.S.; Seely, G.R. Ann. N.Y. Acad. Sci. 206, 649–669 (1973).

    Article  CAS  Google Scholar 

  42. Connolly, J.S.; Janzen, A.F.; Samuel, E.B. Photochem. Photobiol. 36, 559–563 (1982).

    Article  CAS  Google Scholar 

  43. Connolly, J.S.; Samuel, E.B., Janzen, A.F. ibid. 36, 565–574 (1982).

    CAS  Google Scholar 

  44. Siemiarczuk, A.; McIntosh, A.R.; Ho, T. F.; Stillman, M.J.; Roach, K.J.; Weedon, A.C.; Bolton, J.R.; Connolly, J.S. J. Am. Chem. Soc. 105, 7224–7230 (1983).

    Article  CAS  Google Scholar 

  45. Connolly, J.S.; Marsh, K.L.; Cook, D.R.; Bolton, J.R.; McIntosh, A.R.; Siemiarczuk, A.; Ho, T.-F.; Weedon, A.C. Sci. Papers Inst. Phys. and Chem. Res. (Jpn) 78, 118–128 (1984).

    CAS  Google Scholar 

  46. Mcintosh, A.R.; Bolton, J.R.; Connolly, J.S.; Marsh, K.L.; Cook, D.R.; Ho, T.-F.; Weedon, A.C. J. Phys. Chem. 90, 5640–5646 (1986).

    Article  CAS  Google Scholar 

  47. Connolly, J.S.5 Marsh, K.L.; Cook, D.R.; Bolton, J.R.; McIntosh, A.R.; Weedon, A.C.; Ho, T.-F. (to be submitted).

    Google Scholar 

  48. Gorman, D.S.; Connolly, J.S. Inter. J. Chem. Kinetics V, 977–989 (1973).

    Article  Google Scholar 

  49. McIntosh, A.R.; Siemiarczuk, A.; Bolton, J.R.; Stillman, M.J.; Ho, T.-F.; Weedon, A.C. J. Am. Chem. Soc. 105, 7215–7223 (1983).

    Article  CAS  Google Scholar 

  50. Yamada, S.; Sato, T.; Kano, K.; Ogawa, T. Photochem. Photobiol. 37, 257–262 (1983).

    Article  CAS  Google Scholar 

  51. Bergkamp, M.A.; Dalton, J.; Netzel, T.L. J. Am. Chem. Soc. 104, 253–259 (1982).

    Article  CAS  Google Scholar 

  52. Molecular mechanics calculations30 indicate that the quinone end-group in PEAQ is constrained in terms of the accessible distances between it and the porphyrin. Specifically, the mean edge-to-edge distances between the two moieties calculated for two extreme conformations are 4.4 and 4.9 A, respectively. These calculations address neither the dynamics of torsional motion about the linking bridge nor the most favorable orientation between the two p-ring systems for electron transfer. Both factors may play important roles in determining the rates of electron transfer, in these simple donor-acceptor molecules in fluid solution J.13.14.17.30,32c,33a,35.

    Google Scholar 

  53. Schmidt, J.A.; Liu, J.-Y.; Bolton, J.R.; Gadzekpo, V.; Archer, M.D. (to be submitted).

    Google Scholar 

  54. Connolly, J.S.; Wasielewski, M.R. (unpublished, 1985).

    Google Scholar 

  55. Riddick, J.A.; Bunger, W.B. (eds.) Organic Solvents, Physical Properties and Methods of Purification (3rd ed.) in Techniques of Chemistry (Weissberger, A., ed.), Wiley-Interscience, New York, 1970.

    Google Scholar 

  56. Siders, P.; Cave, R.J.; Marcus, R.A. J. Chem. Phys. 81, 5613–5624 (1984).

    Article  CAS  Google Scholar 

  57. Hush, N.S. Coord. Chem. Rev. 64, 135–157 (1985).

    Article  CAS  Google Scholar 

  58. Heitele, H.; Michel-Beyerle, M.E. J. Am. Chem. Soc. 107, 8286–8288 (1985).

    Article  CAS  Google Scholar 

  59. Gray, H.B. Chem. Soc. Rev. 15, 17–30 (1986).

    Article  CAS  Google Scholar 

  60. Ho, P.S.; Sutoris, C.; Liang, N.; Margoliash, E.; Hoffman, B.M. J. Am. Chem. Soc. 107, 1070–1071 (1985).

    Article  CAS  Google Scholar 

  61. Isied, S.S. Prog. Inorg. Chem. 32, 443–517 (1984).

    Article  CAS  Google Scholar 

  62. Mendon, G.; Miller, J.R.; Simolo, K.; Taylor, K.; Mauk A.G.; English, A.M. ACS Symp. Ser. 307, 150–165 (1986).

    Article  Google Scholar 

  63. Kosower, E.M.; Kanety, H.; Dodluk, H; Striker, G.; Jovin, T; Boni, H.; Huppert, D. J. Phys. Chem. 87, 2479–2484 (1983).

    Article  CAS  Google Scholar 

  64. Kosower, E.M.; Huppert, D. Chem. Phys. Lett. 96, 433–435 (1983).

    Article  CAS  Google Scholar 

  65. Kosower, EM.; J. Am. Chem. Soc. 107, 1114–1118 (1985).

    Article  CAS  Google Scholar 

  66. Sumi, H.; Marcus, R.A. J. Chem. Phys. 84, 4272–4276 (1986).

    Article  CAS  Google Scholar 

  67. Muire, M.; Mendon, G. J. Phys. Chem. 90, 2549–2551 (1986).

    Article  Google Scholar 

  68. Onuchic, J.M.; Beratan, D.N.; Hopfield, J.J. J. Phys. Chem. 90, 3707–3721 (1986).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Photoconversion Research Branch, Solar Energy Research Institute, 80401, Golden, Colorado, USA

    John S. Connolly, John K. Hurley, William L. Bell & Kenneth L. Marsh

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  1. John S. Connolly
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  2. John K. Hurley
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  3. William L. Bell
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  4. Kenneth L. Marsh
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Editors and Affiliations

  1. Department of Chemistry “G. Ciamician”, University of Bologna and Institute of FRAE-CNR, Bologna, Italy

    Vincenzo Balzani

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Connolly, J.S., Hurley, J.K., Bell, W.L., Marsh, K.L. (1987). Inter- and Intramolecular Quenching of Porphyrin Excited States by Quinones. In: Balzani, V. (eds) Supramolecular Photochemistry. NATO ASI Series, vol 214. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-3979-0_19

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  • DOI: https://doi.org/10.1007/978-94-009-3979-0_19

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