Abstract
The dynamics of Re(2,2′-bipyridine)(CO)3Cl MLCT state formation and decay were determined after femtosecond UV laser excitation and picosecond pulsed X-ray excitation, in an N,N-dimethylformamide (DMF) solution as well as in its solid form. At room temperature, after UV excitation, this MLCT excited state emits both in DMF solution and in the solid form. Transient absorption spectra were measured in solution at various delay times following excitation by a 160 fs, 390 nm laser pulse. There was a prompt absorption increase at around 460 nm occurring within the pump probe convolution (<1 ps), which was assigned to the formation of the 3MLCT state. This transient absorbance was constant over 100 ps. In contrast to the solution state, in the solid state, the emission maximum slightly red-shifts with increasing time after laser excitation. In both solid and solution the emission rises within the system response time. The solid sample exhibited a 1.4 ns emission decay that was not observed for the solution sample. The emission rise from a solid sample after 20 ps pulsed X-ray excitation was significantly slower than the system’s time resolution. It is proposed that kinetically energetic electrons are ejected following X-ray induced ionisation, creating ionised tracks in which energetic cations and electrons take time to recombine yielding delayed 3MLCT states that emit.
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References
A. Mozumunder, Fundamentals of Radiation Chemistry, Academic Press, San Diego, San Francisco, New York, Boston, London, Sydney, Tokyo, 1999, p. 361.
A. Barkatt and W. Sousanpour, Gamma radiolysis of aqueous media and its effects on the leaching processes of nuclear waste disposal materials, Nucl. Technol., 1983, 60, 2, 218–227.
S. Sunder and H. Christensen, Gamma radiolysis of water solutions relevant to the nuclear-fuel waste management program, Nucl. Technol., 1993, 104, 3, 403–417.
P. A. Rodnyi, Progress in fast scintillators, Radiat. Meas., 2001, 33, 605–614.
W. W. Moses and S. E. Derenzo, Prospects for time-of-flight PET using LSO scintillator, IEEE Trans. Nucl. Sci., 1999, 46, 474–478.
G. Knoll, Radiation Detection and Measurement, Wiley, New York, 3rd edn., 1999.
K. Kleinknecht, Detectors for Particle Radiation, 2nd edn., Cambridge University Press, Cambridge, UK, 1998.
E. Garcia Villora, K. Hatanaka, H. Odaka, T. Sugawara, T. Miura, H. Fukumura and T. Fukuda, Luminescence of undoped β-Ga2O3 single crystals excited by picosecond X-ray and sub-picosecond UV pulses, Solid State Commun., 2003, 127, 385–388.
K. Hatanaka, T. Miura, H. Odaka, H. Ono and H. Fukumura, Various methods for X-ray pulse generation using a femtosecond laser and their potential for time-resolved X-ray analyses, Bunseki Kagaku, 2003, 52, 6, 373–381.
S. E. Derenzo, W. W. Moses, S. C. Blankespoor, M. Ito and K. Oba, Design of a pulsed X-ray system for fluorescent lifetime measurements with a timing accuracy of 109 ps, IEEE Trans. Nucl. Sci., 1994, 41, 3, 629–631.
S. C. Blankespoor, S. E. Derenzo, W. W. Moses, C. S. Rossington, M. Ito and K. Oba, Characterization of a pulsed X-ray source for fluorescent lifetime measurements, IEEE Trans. Nucl. Sci., 1994, 41, 4, 698–702.
L. Papadopoulos, Rise time of scintillation emission in inorganic and organic scintillators, Nucl. Instrum. Methods Phys. Res., Sect. A, 1997, 401, 322–328.
D. L. Horrocks, High-resolution scintillation spectra obtained with nanosecond pulses of 3 MeV electrons, Photochem. Photobiol., 1972, 15, 2, 239–239.
G. Porter and J. W. Boag, Flash photolysis and pulsed radiolysis, Chem. Ind. (London), 1964, 21, 887–887.
G. Scholes, M. Simic, G. E. Adams, J. W. Boag and B. D. Michael, Pulsed radiolysis of cyclohexane solutions - evidence for reactions of electrons, Nature, 1964, 204, 496, 1187–1187.
C. H. Marshall, Pulsed radiolysis and flash spectroscopy studies on amino acid solutions, Phys. Med. Biol., 1966, 11, 1, 177–177.
A. Mozumunder, Fundamentals of Radiation Chemistry, Academic Press, San Diego, San Francisco, New York, Boston, London, Sydney, Tokyo, 1999, pp. 156, 159 and 160.
V. A. Pustovarov, A. L. Krymov and E. I. Zinin, Time resolved luminescence of scintillation crystals under excitation by high-intensity synchrotron radiation, Nucl. Instrum. Methods Phys. Res., Sect. A, 1995, 359, 336–338.
V. A. Pustovarov, A. L. Krymov and B. V. Shulgin, Some peculiarities of the luminescence of inorganic scintillators under excitation by high-intensity synchroton radiation, Rev. Sci. Instrum., 1992, 63, 6, 3521–3522.
N. Y. Kirikova, V. E. Klimenko, V. A. Kozlov, V. N. Makhov, N. M. Khaidukov and T. V. Uvarova, Cross luminescence of several complex fluorides excited by synchrotron-radiation, Nucl. Instrum. Methods Phys. Res., Sect. A, 1995, 359, 351–353.
Von H. Bethe, Zur Theorie des Durchgangs schneller Korpuskularstrahlen durch Materie, Ann. Phys., 1930, 5, 325–400.
A. J. Lees, Luminescence properties of organometalic complexes, Chem. Rev., 1987, 87, 711–743.
M. S. Wrighton and D. L. Morse, The nature of the lowest excited state in tricarbonyl-1,10-phenantholinerhenium(i) and related complexes, J. Am. Chem. Soc., 1974, 96, 998–1003.
J. V. Casper and T. J. Meyer, Application of the energy gap law to nonradiative, excited-state decay, J. Phys. Chem., 1983, 87, 952–957.
W. K. Smothers and M. S. Wrighton, Raman-spectroscopy of electronic excited organometallic complexes - a comparison of the metal to 2,2′-bipyridine charge-transfer state of FAC-(2,2′-bipyridine) tricarbonylhalorhenium and tris(2,2′-bipyridine) ruthenium(ii), J. Am. Chem. Soc., 1983, 105, 1067–1069.
K. Kalyanasundaram, Luminescence and redox reactions of the metal-to-ligand charge-transfer excited state of tricarbonylchloro-(polypyridyl) rhenium(i) complexes, J. Chem. Soc., Faraday Trans., 1986, 2, 82, 2401–2415.
L. A. Worl, R. Duesing, P. Chen, L. D. Ciana and T. J. Meyer, Photophysical properties of polypyridyl carbonyl complexes of rhenium(i), J. Chem. Soc., Dalton Trans., 1991, 849–858.
M. W. George, F. P. A. Johnson, J. R. Westwell, P. M. Hodges and J. J. Turner, Excited state properties and reactivity of [ReCl(CO)3(2,2′-bipy)] (2,2′-bipy =2,2′-bipyridyl) studied by time-resolved infrared spectroscopy, J. Chem. Soc., Dalton Trans., 1993, 2977–2979.
D. R. Striplin and G. A. Crosby, Nature of the emitting 3MLCT manifold of rhenium(i) (diimine) (CO)3Cl complexes, Chem. Phys. Lett., 1994, 221, 426–430.
C. W. E. Van Eijk, Cross-luminescence, J. Lumin., 1994, 60/61, 930–935.
K-C. Tang, K. L. Liu, I-C. Chen, Rapid intersystem crossing in highly phosphorescent iridium complexes, Chem. Phys. Lett., 2004, 386, 437–441.
A. Vlcek, Jr., The life and times of excited states of organometallic and coordination compounds, Coord. Chem. Rev., 2000, 200–202, 933–977.
P. Kubelka and F. Munk, Ein Beitrag zur Optik der Farbanstriche, Z. Tech. Phys., 1931, 12, 593–601.
M. Ichikawa, H. Fukumura and H. Masuhara, Ultrafast electron-transfer and recombination processes on copper phthalocynine solid/water interface as revealed by picosecond regular reflection spectroscopy, J. Phys. Chem., 1995, 99, 12072–12075.
D. Liljequist, A simple calculation of inelastic mean free-path and stopping power for 50 eV–50 keV electrons in solids, J. Phys. D: Appl. Phys., 1983, 16, 1567–1582.
F. Salvat and J. D. Martinez, R Mayol and J Parellada, A simple model fro electron-scattering-inelastic-collisions, J. Phys. D: Appl. Phys., 1985, 18, 299–315.
B. L. Henke, E. M. Gullikson and J. C. Davis, X-ray interactions: photoabsorption, scattering, transmission and reflection at E = 50–30000 eV, Z = 1–92, Atomic Data and Nuclear Data Tables, 1993, 54, 2, 181–342.
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Dedicated to Professor Hiroshi Masuhara on the occasion of his 60th birthday.
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Zhao, L., Odaka, H., Ono, H. et al. Dynamics of Re(2,2′-bipyridine)(CO)3Cl MLCT formation and decay after picosecond pulsed X-ray excitation and femtosecond UV excitation. Photochem Photobiol Sci 4, 113–117 (2005). https://doi.org/10.1039/b409936b
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DOI: https://doi.org/10.1039/b409936b