Skip to main content
SpringerLink
Log in

Solvent dependent photophysics of fac-[Re(CO)3(11,12-X2dppz)(py)]+ (X = H, F or Me)

  • Paper
  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

The photophysical properties of [Re(CO)3(dppz)(py)]+ (dppz = dipyrido-[3,2-a:2′,3′-c] phenazine) (1) and its 11,12 substituted derivatives [Re(CO)3(dppzMe2)(py)]+ (2) and [Re(CO)3(dppzF2)(py)]+ (3) have been examined in organic and aqueous environments using phosphorescence and picosecond transient visible and infrared absorption spectroscopic methods. The roles of the intraligand IL(π-π*) and metal-to-ligand charge transfer MLCT(phz) excited states are evaluated and used to explain the major effect of difluoro-substitution, which is particularly remarkable in water, where the excited state of [Re(CO)3(dppzF2)(py)]+ (3) is strongly quenched.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. See Coord. Chem. Rev., 2004, 248, pp. 1161–1530, special issue dedicated to Dye Sensitized Solar Cells

  2. M. Grätzel, Nature, 2001, 414, 338.

    Article  Google Scholar 

  3. R. J. Forster, T. E. Keyes and J. G. Vos, Interfacial Supramolecular Assemblies, Wiley, London and New York, 2003, ch. 6.

    Google Scholar 

  4. J.-M. Lehn, Supramolecular Chemistry. Concept and Perspectives, VCH, New York, 1995, ch. 8.

    Book  Google Scholar 

  5. V. Balzani, M. Venturi and A. Credi, Molecular Devices and Machines, Wiley-VCH, Weinheim, 2003

    Google Scholar 

  6. V. Balzani, P. Ceroni, M. Maestri, C. Saudan and V. Vicinelli, Light-harvesting dendrimers, Top. Curr. Chem., 2003, 228, 159.

    Article  CAS  Google Scholar 

  7. K. E. Erkkila, D. T. Odom and J. K. Barton, Recognition and reaction of metallointercalators with DNA, Chem. Rev., 1999, 99, 2777.

    Article  CAS  Google Scholar 

  8. C. Moucheron, A. Kirsch-De Mesmaeker and J. M. Kelly, Photophysics and Photochemistry of Metal Polypyridyl and Related Complexes with Nucleic Acids, Struct. Bonding, 1998, 92, 163.

    Article  CAS  Google Scholar 

  9. B. Nordén, P. Lincoln, B. Åkerman and E. Tuite, DNA interactions with substitution-inert transition metal ion complexes, Metal Ions Biol. Syst., 1996, 33, 177.

    Google Scholar 

  10. C. Metcalfe and J. A. Thomas, Kinetically inert transition metal complexes that reversibly bind to DNA, Chem. Soc. Rev., 2003, 32, 215.

    Article  CAS  Google Scholar 

  11. M. J. Clarke, Coord. Chem. Rev., 2003, 236, 209.

    Article  CAS  Google Scholar 

  12. A. E. Friedman, J. C. Chambron, J. P. Sauvage, N. J. Turro and J. K. Barton, Molecular light switch for DNA-Ru(bpy)2(dppz)2+, J. Am. Chem. Soc., 1990, 112, 4960.

    Article  CAS  Google Scholar 

  13. J. Fees, W. Kaim, M. Moscherosch, W. Matheis, J. Klima, M. Krejcik and S. Zalis, Electronic structure of the molecular light switch [Ru(bpy)2(dppz)]2+ (dppz = dipyrido[3,2-A-2′,3′-C]phenazine)-cyclic voltametric, UV Vis and EPR ENDOR study of multiply reduced complexes and ligands, Inorg. Chem., 1993, 32, 166.

    Article  CAS  Google Scholar 

  14. M. K. Brennaman, J. H. Alstrum-Acevedo, C. N. Fleming, P. Jang, T. J. Meyer and J. M. Papanikolas, Turning the [Ru(bpy)2dppz]2+ light-switch on and off with temperature, J. Am. Chem. Soc., 2002, 124, 15094

    Article  CAS  Google Scholar 

  15. M. K. Brennaman, T. J. Meyer and J. M. Papanikolas, [Ru(bpy)2dppz]2+ light-switch mechanism in protic solvents as studied through temperature-dependent lifetime measurements, J. Phys. Chem., 2004, 108, 9938.

    Article  CAS  Google Scholar 

  16. J. Olofsson, B. Onfelt and P. Lincoln, Three-state light switch of [Ru(phen)2dppz]2+: Distinct excited-state species with two, one, or no hydrogen bonds from solvent, J. Phys. Chem. A, 2004, 108, 4391

    Article  CAS  Google Scholar 

  17. B. Onfelt, J. Olofsson, P. Lincoln and B. Norden, Picosecond, and steady-state emission of [Ru(phen)2dppz]2+ in glycerol: Anomalous temperature dependence, J. Phys. Chem. A, 2003, 107, 1000

    Article  Google Scholar 

  18. J. Olofsson, L. M. Wilhelmsson and P. Lincoln, Effects of methyl substitution on radiative and solvent quenching rate constants of [Ru(phen)2dppz]2+ in polyol solvents and bound to DNA, J. Am. Chem. Soc., 2004, 126, 15458.

    Article  CAS  Google Scholar 

  19. G. Pourtois, D. Beljonne, C. Moucheron, S. Schumm, A. Kirsch-De Mesmaeker, R. Lazzaroni and J. L. Bredas, Photophysical properties of ruthenium(ii) polyazaaromatic compounds: A theoretical insight, J. Am. Chem. Soc., 2004, 126, 683.

    Article  CAS  Google Scholar 

  20. J. R. Schoonover, G. F. Strouse, P. Y. Chen, W. D. Bates and T. J. Meyer, Application of time-resolved resonance Raman spectroscopy to intramolecular electron transfer, Inorg. Chem., 1993, 32, 2618 au[9a_J. R. Schoonover, G. F. Strouse, R. B. Dyer, W. D. Bates, P. Y. Chen and T. J. Meyer, Application of time-resolved, step-scan Fourier transform infrared spectroscopy to excited-state electronic structure in polypyridyl complexes of rhenium(i), Inorg. Chem., 1996, 35, 273.

    Article  CAS  Google Scholar 

  21. V. W. W. Yam, K. K. W. Lo, K. K. Cheung and R. Y. C. Kong, Synthesis, photophysical properties and DNA binding studies of novel luminescent rhenium(i) complexes-X-ray crystal structure of [Re(dppn)(CO)3(py)](OTF), J. Chem. Soc., Chem. Commun., 1995, 1191

    Google Scholar 

  22. K. K. W. Lo and K. H. K. Tsang, Bifunctional luminescent rhenium(i) complexes containing an extended planar diimine ligand and a biotin moiety, Organometallics, 2004, 23, 3062.

    Article  CAS  Google Scholar 

  23. H. D. Stoeffler, N. B. Thornton, S. L. Temkin and K. S. Schanze, Unusual photophysics of a rhenium(i) dipyridophenazine complex in homogeneous solution and bound to DNA, J. Am. Chem. Soc., 1995, 117, 7119.

    Article  CAS  Google Scholar 

  24. J. Dyer, W. J. Blau, C. G. Coates, C. M. Creely, J. D. Gavey, M. W. George, D. C. Grills, S. Hudson, J. M. Kelly, P. Matousek, J. J. McGarvey, J. McMaster, A. W. Parker, M. Towrie and J. A. Weinstein, The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN: a comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study, Photochem. Photobiol. Sci., 2003, 2, 542.

    Article  CAS  Google Scholar 

  25. M. R. Waterland and K. C. Gordon, Electronic absorption, resonance Raman and excited-state resonance Raman spectroscopy of rhenium(i) and copper(i) complexes, with substituted dipyrido[3,2-a:2′,3′-c]phenazine ligands, and their electron reduced product, J. Raman Spectrosc., 2000, 31, 243

    Article  CAS  Google Scholar 

  26. A. Flood, R. B. Girling, K. C. Gordon, R. E. Hester, J. N. Moore and M. I. J. Polson, Revealing the chromophoric composition of multichromophoric polypyridyl complexes of Re(i) and Os(ii): a resonance Raman study, J. Raman Spectrosc., 2002, 33, 434.

    Article  CAS  Google Scholar 

  27. N. J. Lundin, P. J. Walsh, S. L. Howell, J. J. McGarvey, A. G. Blackman and K. C. Gordon, Complexes of functionalized dipyrido[3,2-a:2′,3′-c]-phenazine: A synthetic, spectroscopic, structural, and density functional theory study, Inorg. Chem., 2005, 44, 3551

    Article  CAS  Google Scholar 

  28. P. J. Walsh, K. C. Gordon, N. J. Lundin and A. G. Blackman, Photoexcitation in Cu(i) and Re(i) complexes containing substituted dipyrido[3,2-a:2′,3′-c]phenazine: A spectroscopic and density functional theoretical study, J. Phys. Chem. A, 2005, 109, 5933.

    Article  CAS  Google Scholar 

  29. R. López, B. Loeb, D. Striplin, M. Devenney, K. Omberg and T. J. Meyer, Tuning the excited states in fac-[Re(X2dppz)(CO)3(L)]: Intraligand, charge transfer or both?, J. Chil. Chem. Soc., 2004, 49, 149.

    Google Scholar 

  30. M. K. Kuimova, W. Z. Alsindi, J. Dyer, D. C. Grills, O. S. Jina, P. Matousek, A. W. Parker, P. Portius, X. Z. Sun, M. Towrie, C. Wilson, J. Yang and M. W. George, Using picosecond and nanosecond time-resolved infrared spectroscopy for the investigation of excited states and reaction intermediates of inorganic systems, Dalton Trans., 2003, 3996.

    Google Scholar 

  31. J. V. Caspar and T. J. Meyer, Phochemistry of Ru(bpy)32+-solvent effects, J. Am. Chem. Soc., 1983, 105, 5583.

    Article  CAS  Google Scholar 

  32. W. M. Kwok, C. Ma, D. Phillips, P. Matousek, A. W. Parker and M. Towrie, Picosecond time-resolved study of 4-dimethylaminobenzonitrile in polar and nonpolar solvents, J. Phys. Chem. A, 2000, 104, 4188.

    Article  CAS  Google Scholar 

  33. X. Z. Sun, S. M. Nikiforov, J. Yang, C. S. Colley and M. W. George, Nanosecond Time-Resolved Step-Scan FT-IR Spectroscopy in Conventional and Supercritical Fluids Using a Four-Window Infrared Cell, Appl. Spectrosc., 2002, 55, 31.

    Article  Google Scholar 

  34. M. Towrie, D. C. Grills, J. Dyer, J. A. Weinstein, P. Matousek, R. Barton, P. D. Bailey, N. Sabramaniam, W. M. Kwok, C. Ma, D. Phillips, A. W. Parker and M. W. George, Development of a broadband picosecond infrared spectrometer and its incorporation into an existing ultrafast time-resolved resonance Raman, UV-visible, and fluorescence spectroscopic apparatus, Appl. Spectrosc., 2003, 57, 367.

    Article  CAS  Google Scholar 

  35. J. Fees, M. Ketterle, A. Klein, J. Fiedler and W. Kaim, Electrochemical, spectroscopic and EPR study of transition metal complexes of dipyrido[3,2-a:2′,3′-c]phenazin, J. Chem. Soc., Dalton Trans., 1999, 2595.

    Google Scholar 

  36. M. S. Wrighton and D. L. Morse, Nature of lowest excited-state in tricarbonylchloro-1,10-phenanthroline rhenium(i) and related complexes, J. Am. Chem. Soc., 1974, 96, 998.

    Article  CAS  Google Scholar 

  37. P. Glyn, M. W. George, P. M. Hodges and J. J. Turner, Fast Time-resolved IR Studies of the Excited States of Co-ordination Compounds: Direct Observation of Intramolecular Charge Transfer, J. Chem. Soc., Chem. Commun., 1989, 1655.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. School of Chemistry, University of Nottingham, University Park, Nottingham, UK, NG7 2RD

    Joanne Dyer, David C. Grills & Michael W. George

  2. School of Chemistry and School of Physics, University of Dublin, Trinity College, Dublin 2, Ireland

    Caitriona M. Creely, J. Carlos Penedo, Sarah Hudson & John M. Kelly

  3. Central Laser Facility, CCLRC Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire, UK, OX11 0QX

    Pavel Matousek, Anthony W. Parker & Michael Towrie

Authors
  1. Joanne Dyer
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Caitriona M. Creely
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. J. Carlos Penedo
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. David C. Grills
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Sarah Hudson
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Pavel Matousek
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Anthony W. Parker
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Michael Towrie
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. John M. Kelly
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Michael W. George
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Michael W. George.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Dyer, J., Creely, C.M., Penedo, J.C. et al. Solvent dependent photophysics of fac-[Re(CO)3(11,12-X2dppz)(py)]+ (X = H, F or Me). Photochem Photobiol Sci 6, 741–748 (2007). https://doi.org/10.1039/b618651c

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/b618651c

Search

Navigation