Skip to main content
SpringerLink
Log in

Solvent effect for ruthenium porphyrin

  • Research Paper
  • Femtochemistry, Femtobiology and Femtophysics
  • Published:
Science China Physics, Mechanics and Astronomy Aims and scope Submit manuscript

Abstract

Relaxation of electronic excited-state and vibrational dynamics in the electronic excited state in RuII(TPP)(CO) [TPP=tetraphenylporphyrin] dissolved in N2 bubbled benzene, O2 bubbled benzene, N2 bubbled chloroform and N2 bubbled acetone were clarified using a sub-5fs laser pulse. The result showed that the transition energy from the 1Qx states, consisting of the 1Qx(1,0)(π,π*) state (existing at 18800 cm−1) and 1Qx(0,0)(π,π*) state (existing at 17800 cm−1), to the 1M state of six-coordinated ruthenium complex is lower than that of the five-coordinated ruthenium complex. The intersystem crossing 1Qx(0,0)(π,π*)→3(d,π*) in the five-coordinate RuII(TPP)(CO) in the solution was found to take place in about 1 ps.

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

    Article  Google Scholar 

  2. Juris A, Balzani V, Barigelletti F, et al. Ru(II) polypyridine complexes: Photophysics, photochemistry, electrochemistry, and chemiluminescence. Coord Chem Rev, 1988, 84: 85–277

    Article  Google Scholar 

  3. Nazeeruddin M K, Kay A, Rodicio I, et al. Conversion of light to electricity by cis-X2bis(2,2′-bipyridyl-4,4′-dicarboxylate)ruthenium (II) charge-transfer sensitizers (X = Cl-, Br-, I-, CN-, and SCN-) on nanocrystalline titanium dioxide electrodes. J Am Chem Soc, 1993, 115: 6382–6390

    Article  Google Scholar 

  4. Creutz C, Chou M, Netzel T L, et al. Lifetimes, spectra, and quenching of the excited states of polypyridine complexes of iron(II), ruthenium(II), and osmium(II). J Am Chem Soc, 1980, 102: 1309–1319

    Article  Google Scholar 

  5. Bhasikuttan A C, Suzuki M, Nakanishi S, et al. Ultrafast fluorescence detection in tris(2,2′-bipyridine)ruthenium(II) complex in solution: Relaxation dynamics involving higher excited states. J Am Chem Soc, 2002, 124: 8398–8405

    Article  Google Scholar 

  6. McCusker J K. Femtosecond absorption spectroscopy of transition metal charge-transfer complexes. Acc Chem Res, 2003, 36: 876–887

    Article  Google Scholar 

  7. Rillema D P, Nagle J K, Barringer L F, et al. Redox properties of metalloporphyrin excited states, lifetimes, and related properties of a series of para-substituted tetraphenylporphyrine carbonyl complexes of ruthenium(II). J Am Chem Soc, 1981, 103: 56–62

    Article  Google Scholar 

  8. Levine L M A, Holten D. Axial-ligand control of the photophysical behavior of ruthenium(II) tetraphenyl- and octaethylporphyrin. Contrasting properties of metalloporphyrin (π,π*) and (d,π*) excited state. J Phys Chem, 1988, 92: 714–720

    Article  Google Scholar 

  9. Antipas A, Buchler J W, Gouterman M, et al. Porphyrins. 36. Synthesis and optical and electronic properties of some ruthenium and osmium octaethylporphyrins. J Am Chem Soc, 1978, 100: 3015–3027

    Article  Google Scholar 

  10. Prodi A, Indelli M T, Kleverlaan C J, et al. Side-to-face ruthenium porphyrin arrays: Photophysical behavior of dimeric and pentameric systems. Chem Eur J, 1999, 5: 2668–2679

    Article  Google Scholar 

  11. Prodi A, Chiorboli C, Scandola F, et al. Wavelength-dependent electron and energy transfer pathways in a side-to-face ruthenium porphyrin/peryiene bisimide assemble. J Am Chem Soc, 2005, 127: 1454–1462

    Article  Google Scholar 

  12. Iwakura I, Yabushita A, Kobayashi T. Ultrafast vibronic process of Ru porphyrin complex. Euro J Inorg Chem, 2008, 4856–4860

  13. Iwakura I, Kobayashi T, Yabushita A. Direct observation of molecular structural change during intersystem crossing by real-time spectroscopy with a few optical cycle laser. Inorg Chem, 2009, 48: 3523–3528

    Article  Google Scholar 

  14. Baltuska A, Fuji T, Kobayashi T. Visible pulse compression to 4 fs by optical parametric amplification and programmable dispersion control. Opt Lett, 2002, 27: 306–308

    Article  ADS  Google Scholar 

  15. Kadish K M, Chang D. Solvent-binding and solvation effects on the electrode reactions of tetraphenylporphyrin carbonyl complexes of ruthenium(II). Inorg Chem, 1982, 21: 3614–3618

    Article  Google Scholar 

  16. Kadish K M, Leggett D J, Chang D. Investigation of the electrochemical reactivity and axial ligand binding reactions of tetraphenylporphyrin carbonyl complexes of ruthenium(II). Inorg Chem, 1982, 21: 3618–3622

    Article  Google Scholar 

  17. James B R, Dolphin D, Leung T W, et al. Preparation and characterization of some ruthenium(III) porphyrins, including the crystal structure of bromo(octaethylporphinato)(triphenylphosphine)ruthenium (III). Can J Chem, 1984, 62: 1238–1245

    Article  Google Scholar 

  18. Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 03, Revision, D. 02. Wallingford CT: Gaussian, Inc, 2004

    Google Scholar 

  19. Weiss C, Kobayashi H, Gouterman M. Spectra of porphyrins part III. Self-consistent molecular orbital calculations of porphyrin and related ring systems. J Mol Spectrosc, 1965, 16: 415–450

    Article  ADS  Google Scholar 

  20. Gouterman M. The Porphyrins, Vol. 3. New York: Academic Press, 1978

    Google Scholar 

  21. Lim M H, Lippard S J. Fluorescence-based nitric oxide detection by ruthenium porphyrin fluorophore complexes. Inorg Chem, 2004, 43: 6366–6370

    Article  Google Scholar 

  22. Danovich D, Shaik S. Spin-orbit coupling in the oxidative activation of H-H by FeO+. Selection rules and reactivity effects. J Am Chem Soc, 1997, 119: 1773–1786

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Innovative Use of Light and Materials/life, PREST, JST, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan

    Izumi Iwakura

  2. Department of Electrophysics, National Chiao-Tung University, Hsinchu, 300, Taiwan, China

    Atshi Yabushita & Takayoshi Kobayashi

  3. University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo, 182-8585, Japan

    Takayoshi Kobayashi

  4. ICORP, JST, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan

    Takayoshi Kobayashi

  5. Institute of Laser Engineering, Osaka University, 2-6 Yamada-oka, Suita, Osaka, 565-0971, Japan

    Takayoshi Kobayashi

Authors
  1. Izumi Iwakura
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Atshi Yabushita
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Takayoshi Kobayashi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Takayoshi Kobayashi.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Iwakura, I., Yabushita, A. & Kobayashi, T. Solvent effect for ruthenium porphyrin. Sci. China Phys. Mech. Astron. 53, 1005–1012 (2010). https://doi.org/10.1007/s11433-010-3212-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11433-010-3212-1

Keywords

Search

Navigation