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Resonance Raman and lifetime studies on regioselectively deuteriated ruthenium(ii) polypyridyl complexes

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Abstract

Two series of ruthenium(ii) polypyridyl complexes [Ru(bipy)2(phpytr)]+ and [Ru(bipy)2(phpztr)]+ (where Hphpytr = 2-(5-phenyl-1H-[1,2,4]triazol-3-yl)-pyridine and Hphpztr = 2-(5-phenyl-1H-[1,2,4]triazol-3-yl)-pyrazine) are examined by electrochemistry, UV/Vis, emission, resonance Raman, transient resonance Raman and transient absorption spectroscopy, in order to obtain a more comprehensive understanding of their excited state electronic properties. The interpretation of the results obtained is facilitated by the availability of several isotopologues of each of the complexes examined. For the pyridine-1,2,4-triazolato based complex the lowest emissive excited state is exclusively bipy based, however, for the pyrazine based complexes excited state localisation on particular ligands shows considerable solvent and pH dependency.

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References

  1. V. Balzani and F. Scandola, Supramolecular Photochemistry, Ellis Horwood, Chichester, UK, 1991

    Google Scholar 

  2. Supramolecular Photochemistry, ed. V. Balzani, Reidel, Dordrecht, 1997.

    Google Scholar 

  3. K. F. Mongey, J. G. Vos, B. D. MacCraith, C. M. McDonagh, C. Coates and J. J. McGarvey, Photophysics of mixed-ligand polypyridyl ruthenium(ii) complexes immobilised in silica sol-gel monoliths, J. Mater. Chem., 1997, 7, 1473.

    Article  CAS  Google Scholar 

  4. A. Juris, V. Balzani, F. Barigelletti, S. Campagna, P. Belser and A. von Zelewsky, Ru(ii) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence, Coord. Chem. Rev., 1988, 84, 85–277

    Article  CAS  Google Scholar 

  5. K. Kalyanasundaram, Photophysics, photochemistry and solar energy conversion with tris(bipyridyl)ruthenium(ii) and its analogues, Coord. Chem. Rev., 1982, 46, 159–244

    Article  CAS  Google Scholar 

  6. E. A. Seddon and K. R. Seddon, The Chemistry of Ruthenium, Elsevier, Amsterdam, 1984, ch. 15.

    Google Scholar 

  7. H. Yersin, W. Humbs and J. Strasser, Characterization of excited electronic and vibronic states of platinum metal compounds with chelate ligands by highly frequency-resolved and time-resolved spectra, Top. Curr. Chem., 1997, 191, 153–249.

    Article  CAS  Google Scholar 

  8. J. R. Schoonover and G. F. Strouse, Time-resolved vibrational spectroscopy of electronically excited inorganic complexes in solution, Chem. Rev., 1998, 98, 1335–1356.

    Article  CAS  PubMed  Google Scholar 

  9. Y. J. Chang, X. Xu, T. Yabe, S. Yu, D. R. Anderson, L. K. Orman and J. B. Hopkins, Picosecond Raman measurements of electron transfer in the metal-to-ligand charge-transfer excited states of (1,10-phenanthroline)ruthenium(ii) complexes, J. Phys. Chem., 1990, 94, 729–736

    Article  CAS  Google Scholar 

  10. M. Haga, Md. M. Ali, S. Koseki, K. Fujimoto, A. Yoshimura, K. Nozaki, T. Ohno, K. Nakajima and D. J. Stufkens, Proton-induced tuning of electrochemical and photophysical properties in mononuclear and dinuclear ruthenium complexes containing 2,2′-bis(benzimidazol-2-yl)-4,4′-bipyridine: synthesis, molecular structure, and mixed-valence state and excited-state properties, Inorg. Chem., 1996, 35, 3335–3347.

    Article  CAS  Google Scholar 

  11. C. V. Kumar, J. K. Barton, N. J. Turro and I. R. Gould, Time-resolved resonance Raman spectra of polypyridyl complexes of ruthenium(ii), Inorg. Chem., 1987, 26, 1455–1457

    Article  CAS  Google Scholar 

  12. C. V. Kumar, J. K. Barton, I. R. Gould, N. J. Turro and J. van Houten, Energy redistribution and localization in the excited states of ruthenium(ii) polypyridyl complexes, Inorg. Chem., 1988, 27, 648–651

    Article  CAS  Google Scholar 

  13. C. Turro, S. H. Bossman, G. E. Leroi, J. K. Barton and N. J. Turro, Ligand-specific charge localization in the MLCT excited state of Ru(bipy)2(dpphen)2+ monitored by time-resolved resonance Raman spectroscopy, Inorg. Chem., 1994, 33, 1344–1347.

    Article  CAS  Google Scholar 

  14. S. F. McClanahan, R. F. Dallinger, F. J. Holler and J. R. Kincaid, Mixed-ligand poly(pyridine) complexes of ruthenium(ii). Resonance Raman spectroscopic evidence for selective population of ligand-localized 3MLCT excited states, J. Am. Chem. Soc., 1985, 107, 4853–4860

    Article  CAS  Google Scholar 

  15. G. D. Danzer, J. A. Golus and J. R. Kincaid, Resonance Raman and time-resolved resonance Raman evidence for enhanced localization in the 3MLCT states of ruthenium(ii) complexes with the inherently asymmetric ligand 2-(2-pyridyl)pyrazine, J. Am. Chem. Soc., 1993, 115, 8643–8648

    Article  CAS  Google Scholar 

  16. M. Sykora and J. R. Kincaid, Synthetic manipulation of excited state decay pathways in a series of ruthenium(ii) complexes containing bipyrazine and substituted bipyridine ligands, Inorg. Chem., 1995, 34, 5852–5856.

    Article  CAS  Google Scholar 

  17. E. Krausz, G. Moran and H. Riesen, Temperature-dependent lifetimes, MCPL and shifts of the luminescence in the materials [Ru(bipy)x(bipy-d83−x]2+, x = 0-3, in dilute systems, Chem. Phys. Lett., 1990, 165, 401–406

    Article  CAS  Google Scholar 

  18. H. Riesen, L. Wallace and E. Krausz, Deuteration effects in the lowest-excited 3MLCT States of [Ru(bipy)3]2+ in [Zn(bipy)3](ClO4, J. Phys. Chem., 1995, 99, 16807–16809

    Article  CAS  Google Scholar 

  19. H. Riesen, L. Wallace and E. Krauz, Dynamical processes in the lowest-excited triplet metal-to-ligand charge transfer states of ruthenium and osmium diimine complexes in crystals, Int. Rev. Phys. Chem., 1997, 16, 291–359.

    Article  CAS  Google Scholar 

  20. P. K. Mallick, G. D. Danzer, D. P. Strommen and J. R. Kincaid, Vibrational spectra and normal-coordinate analysis of tris(bipyridine)ruthenium(ii), J. Phys. Chem., 1988, 92, 5628–5634

    Article  CAS  Google Scholar 

  21. K. Maruszewski, K. Bajdor, D. P. Strommen and J. R. Kincaid, Position-dependent deuteration effects on the nonradiative decay of the 3MLCT state of tris(bipyridine)ruthenium(ii). An experimental evaluation of radiationless transition theory, J. Phys. Chem., 1995, 99, 6286–6293.

    Article  CAS  Google Scholar 

  22. R. Hage, J. G. Haasnoot, J. Reedijk, R. Wang and J. G. Vos, Mononuclear and dinuclear ruthenium complexes with triazole containing ligands; fine-tuning of the spectroscopic properties, Inorg. Chem., 1991, 30, 3263–3269

    Article  CAS  Google Scholar 

  23. H. P. Hughes, D. Martin, S. Bell, J. J. McGarvey and J. G. Vos, Photophysical and photochemical properties of dinuclear ruthenium(ii) complexes containing 2,2′-bipyridine and 1,10-phenanthroline moieties, Inorg. Chem., 1993, 32, 4402–4408

    Article  CAS  Google Scholar 

  24. C. G. Coates, T. E. Keyes, J. J. McGarvey, H. P. Hughes, J. G. Vos and P. M. Jayaweera, Time-resolved spectroscopic studies of the influence of the electronic environment on the charge-transfer excited states of mono- and di-nuclear Ru(ii) complexes, Coord. Chem. Rev., 1998, 171, 323–330

    Article  CAS  Google Scholar 

  25. C. G. Coates, T. E. Keyes, H. P. Hughes, P. M. Jayaweera, J. J. McGarvey and J. G. Vos, Resonance Raman and spectroelectrochemical investigation of the location of the lowest excited state in mono- and dinuclear ruthenium(ii) complexes containing pyrazine moieties, J. Phys. Chem. A, 1998, 102, 5013–5018

    Article  CAS  Google Scholar 

  26. S. Fanni, T. E. Keyes, C. M. O’Connor, H. P. Hughes, R. Wang and J. G. Vos, Excited-state properties of ruthenium(ii) polypyridyl complexes containing asymmetric triazole ligands, Coord. Chem. Rev., 2000, 208, 77–86.

    Article  CAS  Google Scholar 

  27. H. E. Nieuwenhuis, J. G. Haasnoot, R. Hage, J. Reedijk, T. L. Snoeck, D. J. Stufkens and J. G. Vos, pH control of the photophysical properties of ruthenium complexes containing 3-(pyrazin-2-yl)-1,2,4-triazole ligands, Inorg. Chem., 1991, 30, 48–54.

    Article  CAS  Google Scholar 

  28. Note that coordination is possible via the N2 or N4 position of the triazole moiety, leading to coordination isomers. However the present study focuses on the N2 isomers only.

  29. W. R. Browne and J. G. Vos, The effect of deuteriation on the emission lifetime of inorganic compounds, Coord. Chem. Rev., 2001, 219, 761–787

    Article  Google Scholar 

  30. W. R. Browne, P. Passaniti, M. T. Gandolfi, R. Ballardini, W. Henry, A. Guckian, N. O’Boyle, J. J. McGarvey and J. G. Vos, Probing inter-ligand excited state interaction in homo and heteroleptic ruthenium(ii) polypyridyl complexes using selective deuteriation, Inorg. Chim. Acta, 2007, 360, 1183–1190.

    Article  CAS  Google Scholar 

  31. B. P. Sullivan, D. J. Salmon and T. J. Meyer, Mixed phosphine 2,2′-bipyridine complexes of ruthenium, Inorg. Chem., 1978, 17, 3334–3341.

    Article  CAS  Google Scholar 

  32. R. Wang, J. G. Vos, R. H. Schmehl and R. Hage, pH Control of photoreactivity of ruthenium(ii) pyridyltriazole complexes: photoinduced linkage isomerism and photoanation, J. Am. Chem. Soc., 1992, 114, 1964–1970.

    Article  CAS  Google Scholar 

  33. W. R. Browne, C. M. O’Connor, J. S. Killeen, A. L. Guckian, M. Burke, P. James, M. Burke and J. G. Vos, Routes to regioselective deuteriation of heteroaromatic compounds, Inorg. Chem., 2002, 41, 4245–4251.

    Article  CAS  PubMed  Google Scholar 

  34. W. R. Browne, D. Hesek, J. F. Gallagher, C. M. O’Connor, J. S. Killeen, F. Aoki, H. Ishida, Y. Inoue, C. Villani and J. G. Vos, Structural and photophysical characterisation of coordination and optical isomers of mononuclear ruthenium(ii) polypyridyl 1,2,4-triazole complexes, Dalton Trans., 2003, 2597–2602.

    Google Scholar 

  35. W. R. Browne, C. M. O’Connor, C. Villani and J. G. Vos, Separation and photophysical properties of the LL, dl, LD and DD stereoisomers of a dinuclear ruthenium(ii) complex, Inorg. Chem., 2001, 40, 5461–5464.

    Article  CAS  PubMed  Google Scholar 

  36. C. G. Coates, L. Jacquet, J. J. McGarvey, S. E. J. Bell, A. H. R. Al-Obaidi and J. M. Kelly, Resonance Raman probing of the interaction between dipyridophenazine complexes of Ru(ii) and DNA, J. Am. Chem. Soc., 1997, 119, 7130–7136

    Article  CAS  Google Scholar 

  37. C. G. Coates, J. Olofsson, M. Coletti, J. J. McGarvey, B. Onfelt, P. Lincoln, B. Norden, E. Tuite, P. Matousek and A. W. Parker, Picosecond time-resolved resonance Raman probing of the light-switch states of [Ru(Phen)2dppz]2+, J. Phys. Chem. B, 2001, 105, 12653–12664.

    Article  CAS  Google Scholar 

  38. W. R. Browne, N. M. O’Boyle, W. Henry, A. L. Guckian, S. Horn, T. Fett, C. M. O’Connor, M. Duati, L. De Cola, C. G. Coates, K. L. Ronayne, J. J. McGarvey and J. G. Vos, Ground- and excited-state electronic structure of an emissive pyrazine-bridged ruthenium(ii) dinuclear complex, J. Am. Chem. Soc., 2005, 127, 1229–1241.

    Article  CAS  PubMed  Google Scholar 

  39. J. V. Caspar, E. M. Kober, B. P. Sullivan and T. J. Meyer, Application of the energy gap law to the decay of charge-transfer excited states, J. Am. Chem. Soc., 1982, 104, 630–632.

    Article  CAS  Google Scholar 

  40. P. G. Bradley, N. Kress, B. A. Hornberger, R. F. Dallinger and W. H. Woodruff, Vibrational spectroscopy of the electronically excited state. 5. Time-resolved resonance Raman study of tris(bipyridine)ruthenium(II) and related complexes. Definitive evidence for the “localized” MLCT state, J. Am. Chem. Soc., 1981, 103, 7441–7446.

    Article  CAS  Google Scholar 

  41. J. G. Vos, Excited-state acid-base properties of inorganic compounds, Polyhedron, 1992, 11, 2285–2299.

    Article  CAS  Google Scholar 

  42. T. E. Keyes, F. Weldon, E. Müller, P. Pechy, M. Grätzel and J. G. Vos, Application of deuteriation to determine the location of the emitting state in mixed-ligand RuII polypyridyl complexes, J. Chem. Soc., Dalton Trans., 1995, 2705–2706.

    Google Scholar 

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Author notes

  1. Wesley R. Browne

    Present address: Stratingh Institute, Organic and Molecular Inorganic Chemistry, University of Groningen, Nijenborgh 4, 9747AG, Groningen, The Netherlands

Authors and Affiliations

  1. National Centre for Sensor Research, School of Chemical Sciences, Dublin City University, Dublin 9, Ireland

    Wesley R. Browne, William Henry & Johannes G. Vos

  2. Dipartimento di Chimica “G.Ciamician”, University of Bologna Via Selmi 2, 40126, Bologna, Italy

    Paolo Passaniti, Maria Teresa Gandolfi & Roberto Ballardini

  3. School of Chemistry, Dublin Institute of Technology, Kevin Street, Dublin 8, Ireland

    Christine M. O’Connor

  4. School of Chemistry and Chemical Engineering, Queen’s University, Belfast, BT9 5AG, Ireland

    Clare Brady & John J. McGarvey

  5. Andor Technology, 7 Millennium Way, Springvale Business Park, Belfast, BT12 7AL, Ireland

    Colin G. Coates

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  1. Wesley R. Browne
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Correspondence to John J. McGarvey.

Additional information

This paper was published as part of the special issue to commemorate the 70th birthday of Vincenzo Balzani.

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Browne, W.R., Henry, W., Passaniti, P. et al. Resonance Raman and lifetime studies on regioselectively deuteriated ruthenium(ii) polypyridyl complexes. Photochem Photobiol Sci 6, 386–396 (2007). https://doi.org/10.1039/b613471h

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