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Photoredox and Sensitization Processes Involving Transition Metal Polypyridine Complexes

  • Chapter
Photosensitization and Photocatalysis Using Inorganic and Organometallic Compounds

Part of the book series: Catalysis by Metal Complexes ((CMCO,volume 14))

Abstract

2,2’-bipyridine, 1,10-phenanthroline and related polypyridine ligands are unique in their ability to complex to a large number of transition metal ions across the periodic table. The complexation equilibria and redox reactivity of these complexes have been the focus of experimental investigations for many years [1–3]. Complexes of ions with d6 electronic configuration are attractive from photophysical and photochemical properties point of view. Systematic studies started with the first reports of room-temperature luminescence from Ru(bpy)3 2+ in 1959 by Paris and Brandt[4]. This was followed by key observations by Adamson et al. in the early seventies [5,6] that Ru(bpy)3 2+ could photosensitize aquation of Pt(II)-cyano complexes (eq.1) and redox decomposition of Co(III)-ammine complexes (eq.2):

$$PtC{I_4}^{{2_ - }} + {H_2}O\xrightarrow[{hv}]{{Ru(bpy){3^{2 + }}}}PtC{I_3}{({H_2}O)^ - } + C{I^ - }$$
(1)
$$Co{(N{H_3})_5}B{r^{2 + }}\xrightarrow[{hv}]{{Ru(bpy){3^{2 + }}}}C{o_{aq}}^{3 + } + 5N{H_3} + B{r^ - }$$
(2)

Around this time Fujita and Kobayashi [7] reported detection of phosphorescence of Cr(III) upon excitation of the Ru(bpy)3 2+ band in the double salts composed of CrL6 3− and Ru(bpy)3 2+ (L = CN, ox/2,…)

$$Ru(bhy){3^{2 + *}} \ldots CrL{6^{3 - }} \to Ru{(bhy)_3}^{2 + } \ldots CrL{6^{3 - *}}$$
(3)

Possible intermolecular energy / electron transfer processes were invoked to explain the sensitization. The mechanistic propositions were soon verified by additional luminescence quenching, flash photolysis and sensitization studies.

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References

  1. W.W. Brandt, F.P. Dwyer and E.C. Gyarfas: Chem. Rev., 54, 959 (1954)

    Article  CAS  Google Scholar 

  2. W.R. McWhinnie and J.D. Miller: Adv. Inorg. Chem., Radiochem., 12, 135 (1969)

    CAS  Google Scholar 

  3. E.C. Constable: Adv. Inorg. Chem.Radiochem., 34, 1 (1989); ibid., 30, 69 (1986)

    Article  Google Scholar 

  4. T.P. Paris and W.W. Brandt: J. Am.Chem.Soc., 81, 5001 (1959)

    Article  CAS  Google Scholar 

  5. J.N. Demas and A.W. Adamson: J, Am.Chem.Soc., 93, 1800 (1971)

    Google Scholar 

  6. H.D. Gafney and A.W. Adamson: J. Am.Chem.Soc., 94, 8238 (1972)

    Article  CAS  Google Scholar 

  7. I. Fujita and H. Kobayashi: J. Chem. Phys., 52, 4904 (1970); ibid., 59, 2902 (1972)

    Google Scholar 

  8. A. Juris, V. Balzani, F. Barigelletti, S. Campagna, P. Belser and A. von Zelewsky: Coord. Chem.Rev., 84, 85 (1988)

    Article  CAS  Google Scholar 

  9. R.A. Krause: Struc. Bonding, 67, 1 (1987)

    Article  Google Scholar 

  10. N. Sutin and C. Creutz: Pure Appl. Chem., 52, 2717 (1980)

    Article  CAS  Google Scholar 

  11. K. Kalyanasundaram: Coord. Chem.Rev., 46, 159 (1982)

    Article  CAS  Google Scholar 

  12. T.J. Meyer: Pure Appl. Chem., 58, 1193 (1986)

    Article  Google Scholar 

  13. K. Kalyanasundaram: Photochemistry of Polypyridine and Porphyrin Complexes, Academic Press, London, 1992

    Google Scholar 

  14. M. Nishizawa, T.M. Suzuki, R.J. Watts and P.C. Ford: Inorg. Chem., 23, 1837 (1984)

    Article  CAS  Google Scholar 

  15. M.E. Frink, S.D. Sprouse, H.A. Goodwin, R.J. Watts and P.C. Ford: Inorg. Chem., 27, 1283 (1988)

    Article  CAS  Google Scholar 

  16. F. Barigelletti, P.Belser, A. von Zelewsky and V. Balzan: J. Phys. Chem., 89, 3680 (1985)

    Article  CAS  Google Scholar 

  17. a) A.K. Ichinaga, J.R. Kirchhoff, D.R. McMillin, C.O. Dietrich-Buchecker, P.A. Mamot and J-.P. Sauvage: Inorg. Chem., 26, 4290 (1987); b) C.C. Phifer and D.R. McMillin: Inorg. Chem., 25, 1329 (1986)

    Article  Google Scholar 

  18. R.J. Watts: Inorg. Chem., 20, 2302 (1981); b) R.J. Watts and D. Missimer: J. Am. Chem.Soc., 100, 5350 (1978); c) R. Ballardini, G. Varani, L. Moggi and V. Balzani: J. Am. Chem.Soc., 96, 7123 (1974)

    Article  Google Scholar 

  19. M.T. Indelli and F. Scandola: Inorg. Chem., 29, 3056 (1990)

    Article  CAS  Google Scholar 

  20. K. Kalyanasundaram, M. Grätzel and Md. K. Nazeeruddin: J. Phys. Chem., 96, 5865 (1992)

    Article  CAS  Google Scholar 

  21. A.M. Ghiath, L.S. Forster and J.V. Rund: Inorg. Chem., 26, 2493 (1987)

    Article  Google Scholar 

  22. C.-T. Lin, W. Bottcher, M. Chou, C. Creutz and N. Sutin: J. Am. Chem.Soc., 98, 6536 (1976)

    Article  CAS  Google Scholar 

  23. K. Kalyanasundaram and Md. K. Nazeeruddin: Chem. Phys. Lett., 193, 292 (1992)

    Article  CAS  Google Scholar 

  24. M. T Indelli, C.A. Bignozzi, A. Marconi and F. Scandola, J. Am. Chem.Soc., 110, 7381 (1988)

    Article  CAS  Google Scholar 

  25. J.V. Caspar, E.M. Kober, B. P. Sullivan and T.J. Meyer: J. Am. Chem.Soc., 104, 630 (1982); b) J.V. Caspar and T.J. Meyer: J. Phys. Chem., 87, 952 (1983)

    Article  CAS  Google Scholar 

  26. R.J. Crutchley and A.B.P. Lever: J. Am. chem.Soc., 102, 7129 (1980); Inorg. Chem., 21, 2276 (1982)

    CAS  Google Scholar 

  27. C.K. Ryu and J.N. Endicot:t: Inorg. Chem., 27, 2203 (1988)

    Article  CAS  Google Scholar 

  28. V. Balzani and F. Scandola: Energy Resources Through Photochemistry and Catalysis (M. Grätzel, ed), Academic Press, New York, 1985, ch.1 b) V. Balzani and F. Scandola: Photochemical Conv.Storage Solar Energy (J.S. Connolly, ed.), Academic Press, New York, 1981, ch. 4

    Google Scholar 

  29. D. Rehm and A. Weller: Ber. Bunsenges. Phys. Chem., 73, 834 (1969) b) D. Rehm and A. Weller: Isr. J. Chem., 8, 259 (1970)

    CAS  Google Scholar 

  30. R.A. Marcus: Disc. Faraday Soc.,29, 21 (1960); Ann. Rev. Phys. Chem., 15, 155 (1964); Electrochim.Acta, 13, 995 (1968)

    Article  CAS  Google Scholar 

  31. R.A. Marcus and N. Sutin: Biochem. Biophys. Acta, 811, 265 (1985)

    Article  CAS  Google Scholar 

  32. C. Creutz, M. Chou, T.L. Netzel, M. Okumura and N. Sutin: J. Am. Chem.Soc., 102, 1309 (1980)

    Article  CAS  Google Scholar 

  33. A. Juris, M.F. Manfrin, M. Maestri and N. Serpone: Inorg. Chem., 17, 2258 (1978)

    Article  CAS  Google Scholar 

  34. C. Creutz, B. Brunschwig and N. Sutin: J. Am. Chem. Soc., 101, 1297 (1979)

    Article  CAS  Google Scholar 

  35. P. Natarajan and J.F. Endicott: J. Phys. Chem., 77, 971, 1823 (1973)

    Article  CAS  Google Scholar 

  36. G. Navon and N. Sutin: Inorg. Chem., 13, 2159 (1974)

    Article  CAS  Google Scholar 

  37. D. Sandrini, M.T. Gandolfi, M. Maestri, F. Boletta and V. Balzan: Inorg. Chem., 23, 3017 (1984)

    Article  CAS  Google Scholar 

  38. a) K.R. Leopold and A. Haim: Inorg. Chem., 17, 1753 (1978); b) W. Böttcher and A. Haim: J. Am. Chem. Soc., 102, 1564 (1980); c) K. Zahir, W. Böttcher and A. Haim: Inorg. Chem., 23, 3091 (1984)

    Google Scholar 

  39. C.R. Bock, J.A. Connor, A.R. Gutierrez, T.J. Meyer, D.G. Whitten, B.P.Sullivan and J.K. Nagle: J. Am. Chem. Soc., 101, 4815 (1979)

    Article  CAS  Google Scholar 

  40. K. Kalyanasundaram, J. Kiwi and M. Grätzel: Hely. Chim. Acta, 61, 2720 (1978)

    Article  CAS  Google Scholar 

  41. E. Amouyal, B. Zidler, P. Keller and A. Moradpour, Chem. Phys. Lett, 74, 314 (1980)

    Article  CAS  Google Scholar 

  42. a) C. Creutz, A.D. Keller, N. Sutin and A.P. Zipp: J. Am. Chem. Soc., 104, 3618 (1982); b) S.-F. Chan, M. Chou, C. Creutz, T. Matsubara and N. Sutin, J. Am. Chem. Soc., 103, 369 (1981); M.Z. Hoffman: J. Phys. Chem., 92, 3458 (1988)

    Article  Google Scholar 

  43. C-Y. Mok, A.W. Zanella, C. Creutz and N. Sutin: J. Am, Chem. Soc., 23, 2891 (1984)

    CAS  Google Scholar 

  44. a) P.A. Lay, A.W.-H. Mau, W.H.F. Sasse, I.I. Creaser, L. R. Gahan and A.M. Sargeson, Inorg. Chem., 22, 2347 (1983); b) I. G. Creaser, L.R. Gahan, R.J. Geue, A. Launikonis, P.A. Lay, J.D. Lydon, M.G. McCarthy, A.W.-H. Mau, A.M. Sargeson and W.H.F. Sasse, Inorg. Chem., 24, 2671 (1985)

    Google Scholar 

  45. a) V. Houlding, T. Geiger, U. Kölle and M. Grätzel, J. Chem. Soc., Chem. Commun., 681 (1982); b) M.A.R. Scandola, F. Scandola, A. Indelli and V. Balzan, Inorg. Chim. Acta, 76, L67 (1983)

    Google Scholar 

  46. M.A. Haselton, C.-T. Lin, H.A. Schwarz and N. Sutin, J. Am.Chem.Soc., 100, 2383 (1978)

    Article  Google Scholar 

  47. J.E. Baggott and M.J. Pilling: J. Phys. Chem., 84, 3012 (1980)

    Article  CAS  Google Scholar 

  48. M. I. Ferreira and A. Harriman: J. Chem. Soc, Faraday Trans, II,75 874 (1979)

    Google Scholar 

  49. a) M. Neumann-Spallart, K. Kalyanasundaram, C. Grätzel and M. Grätzel: Heiv. Chim.Acta, 63, 1111 (1980); b) H.S. White, W.G. Becker and A.J. Bard: J. Phys. Chem., 88, 1840 (1984)

    Article  Google Scholar 

  50. F. Boletta, A. Juris, M. Maestri and D. Sandrini: Inorg. Chim. Acta, 44, L175 (1980)

    Article  Google Scholar 

  51. G.S. Laurence and V. Balzani: Inorg. Chem., 13, 2976 (1974)

    Article  CAS  Google Scholar 

  52. M. Maestri and M. Grätzel: Ber. Bunsenges. Phys Chem., 81, 504 (1977)

    Article  CAS  Google Scholar 

  53. H. Shioyama, H. Masuhara and N. Mataga: Chem. Phys. Lett., 88, 161 (1982)

    Article  CAS  Google Scholar 

  54. a) T. Olmo and S. Kato: Bull. Chem.Soc., Japan, 57, 3391 (1984); b) T. Olmo, A. Yoshimura and N. Mataga: J. Phys. Chem., 90, 3295 (1986)

    Article  Google Scholar 

  55. R. Ballardini, G. Varani, M.T. Indelli, F. Scandola and V. Balzani: J. Amer. Chem.Soc., 100, 7219 (1978)

    Article  CAS  Google Scholar 

  56. J-.0-. Luong, L. Nadjo and M.S. Wrighton: J. Amer. Chem.Soc., 100, 5790 (1978)

    Article  CAS  Google Scholar 

  57. a) K. Kalyanasundaram: J.C.S. Faraday Trans, II, 82, 2401 (1986); C. Kutal, M.A. Weber, G. Ferraudi and D. Geiger: Organometallics, 4, 2161 (1985); c) C.A. Kutal, A. J. Corbin and G. Ferraudi: Organometallics, 6, 553 (1987)

    Article  Google Scholar 

  58. S.M. Fredericks and M.S. Wrighton: J. Amer. Chem.Soc., 102, 6166 (1980)

    Article  CAS  Google Scholar 

  59. D.P. Summers, J-C. Luong and M. S. Wrighton: J. Amer. Chem.Soc., 103, 5238 (1981)

    Article  CAS  Google Scholar 

  60. a) J. Hawecker, J-M. Lehn and R. Ziessel: J.Chem.Soc.,Chem. Commun., 536 (1983); ibid, 328 (1984); b) B.P. Sullivan, C.M. Bollinger, D.Conrad, W.J. Vining and T.J. Meyer: J.Chem.Soc., Chem. Commun., 1414 (1985)

    Google Scholar 

  61. a) C. Creutz and N. Sutin: Inorg. Chem., 15, 496 (1976); b) C.V. Krishnan, C. Creutz, D. Mahajan, H.A. Schwarz adn N. Sutin: Isr. J. Chem., 22, 98 (1982)

    Google Scholar 

  62. C. Creutz: Inorg. Chem., 17, 1046 (1978)

    Article  CAS  Google Scholar 

  63. E. Pelizzetti, E. Mentasti and E. Pramauro: Inorg. Chem., 15, 2898 (1976)

    Article  CAS  Google Scholar 

  64. C. Creutz, N. Sutin and B. Brunschwig: J. Amer. Chem.Soc., 101, 1297 (1979)

    Article  CAS  Google Scholar 

  65. a) D. Meisel and J. Norris, eds: Photochemical Conversion and Storage of Solar Energy,Academic Press, New York, 1989 and refs. cited therein. b) E. Pelizzetti and M. Schiavello, eds.: Photochemical Conversion and Storage of Solar Energy,Kluwer Academic Publishers, 1991 and refs. cited therein.

    Google Scholar 

  66. K. Kalyanasundaram, J. Kiwi and M. Grätzel: Struc. Bonding, 49, 37 (1981)

    Google Scholar 

  67. K. Kalyanasundaram, M. Grätzel and E. Pelizzetti: Coord. Chem. Rev., 69, 57 (1986)

    Article  Google Scholar 

  68. I.Willner and B. Willner: Photochemical Conversion and Storage of Solar Energy (E. Pelizzetti and M. Schiavello, eds.) Kluwer Academic Publishers, Dordrecht, 1991 and refs. cited therein.

    Google Scholar 

  69. I. Willner and B. Wainer: Top. Curr. Chem., 159, 153 (1991)

    Article  CAS  Google Scholar 

  70. K. Kalyanasundaram, T. Colasis, R. Humphry-Baker, E. Pelizzetti, E. Bami, P. Savarino and M. Grätzel: J. Am. Chem.Soc., 111, 3300 (1989)

    Article  CAS  Google Scholar 

  71. R. Ziessel: Nouv.J. Chim., 7, 613 (1983)

    CAS  Google Scholar 

  72. T.J. Meyer: J. Electrochem. Soc., 131, 221C (1984); b) B.P. Sullivan, M.R: Bruce, t.R. O’Toole, C.M. Bollinger, E. Megehee, H. Thorp and T.J. Meyer in Catalytic Activation of Carbon Dioxide (W. Ayers, ed.), ACS Symposium Series 363, American Chemical Society, Washington, DC, 1988

    Google Scholar 

  73. N. Sabbatini, M.A. Scandola and V. Carassiti: J. Phys. Chem., 77, 1307 (1973)

    Article  CAS  Google Scholar 

  74. N. Sabbatini, M.A. Scandola and V. Balzani J. Phys. Chem., 78, 541 (1974)

    Article  CAS  Google Scholar 

  75. F. Boletta, M. Maestri and V. Balzani: J. Phys. Chem., 80, 2499 (1976)

    Article  Google Scholar 

  76. F. Boletta, A. Rossi, F. Barigelletti, S. Dellonte and V. Balzan: Gazz.Chim.Ital., 111, 155 (1978)

    Google Scholar 

  77. M. T. Indelli, A. Carioli and F. Scandola: J. Phys. Chem., 88, 2685 (1984)

    Article  CAS  Google Scholar 

  78. R. Tamilarasan and J.F. Endicott: J. Phys. Chem., 90, 1027 (1986)

    Article  CAS  Google Scholar 

  79. J.F. Endicott, T. Ramaswami, D.C. Gaswick, R. Tamilarasan, M.J. Herg, G.R. Brubaker and S.C. Pyke: J. Am.Chem.Soc., 105, 5301 (1983)

    Article  CAS  Google Scholar 

  80. N. Serpone, M.A. Jamieson and M.Z. Hoffman: Inorg. Chim.Acta: 31, L447 (1978)

    Article  CAS  Google Scholar 

  81. B. Brunschwig and N. Sutin: J. Am. Chem.Soc., 100, 7568 (1978)

    Article  CAS  Google Scholar 

  82. M.S. Wrighton and J. Markham: J. Phys. Chem., 77, 3042 (1973)

    Article  CAS  Google Scholar 

  83. M.S. Wrighton, L. Pdungsap and D.L. Morse: J. Phys. Chem., 79, 66 (1975)

    Article  CAS  Google Scholar 

  84. C.R. Bock, T.J. Meyer and D. G. Whitten: J.Am.Chem.Soc., 96, 4710 (1974)

    Article  CAS  Google Scholar 

  85. O. Johansen, A.W-.H. Mau and W.H.F. Sasse: Chem.Phys.Lett., 94, 107 (1983); ibid., 94, 113 (1983)

    Google Scholar 

  86. J.Olmsted and T.J. Meyer: J. Phys. Chem., 91, 1649 (1987)

    Article  Google Scholar 

  87. A. Edel, P.A. Marnot and J-P. Sauvage: Nouv. J. Chim., 8, 495 (1984)

    CAS  Google Scholar 

  88. P.A. Grutsch and C. Kutal: J. Am. Chem. Soc., 108, 3108 (1986)

    Article  CAS  Google Scholar 

  89. A. Zakir, J.H. Espenson and A. Bakac: Inorg. Chem., 27, 3144 (1988); b) C.R. Steffan, A.Bakac and J.H. Espenson: Inorg. Chem., 28, 2992 (1989); c) C.A. Simmons, A. Bakac and J.H. Espenson: Inorg. Chem., 28, 581 (1989)

    Article  Google Scholar 

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Kalyanasundaram, K. (1993). Photoredox and Sensitization Processes Involving Transition Metal Polypyridine Complexes. In: Kalyanasundaram, K., Grätzel, M. (eds) Photosensitization and Photocatalysis Using Inorganic and Organometallic Compounds. Catalysis by Metal Complexes, vol 14. Springer, Dordrecht. https://doi.org/10.1007/978-94-017-2626-9_5

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