Ultrafast pump-probe spectroscopy of IrCl_6^2− complex in alcohol solutions

Ultrafast pump-probe spectroscopy (λ(pump) = 400 nm) was applied to study the primary photophysical processes for the IrCl(6)(2-) complex in methanol and ethanol solutions. The excitation to the LMCT 2U(u)' state was followed by formation of an intermediate absorption completely decaying with three characteristic times of 300 fs, ca. 2.5 ps, and 30 ps. The corresponding processes were interpreted as the 2U(u)'*→1U(g)'* electronic transition, vibrational relaxation, and internal conversion to the ground state. Complete recovery of the ground state is consistent with the absence of the photochemical activity of the IrCl(6)(2-) visible LMCT bands.

[1]  J. McCusker,et al.  Vibrational coherence in the excited state dynamics of Cr(acac)3: probing the reaction coordinate for ultrafast intersystem crossing , 2010 .

[2]  Tae Kyu Kim,et al.  Photo-induced spin-state conversion in solvated transition metal complexes probed via time-resolved soft X-ray spectroscopy. , 2010, Journal of the American Chemical Society.

[3]  N. Tkachenko,et al.  Photophysics of IrCl62- complex in aqueous solutions studied by femtosecond pump–probe spectroscopy , 2009 .

[4]  M. Kappes,et al.  Photodissociation dynamics of IrBr6(2-) dianions by time-resolved photoelectron spectroscopy. , 2009, The Journal of chemical physics.

[5]  N. Tkachenko,et al.  Photochemistry of the IrCl62− complex in aqueous solutions in the presence of the bromide anions , 2008 .

[6]  N. Tkachenko,et al.  Primary processes in photophysics and photochemistry of PtBr62- complex studied by femtosecond pump–probe spectroscopy , 2007 .

[7]  K. Tominaga,et al.  Vibrational population relaxation of thiocyanate ion in polar solvents studied by ultrafast infrared spectroscopy , 2006 .

[8]  L. Forster Intersystem crossing in transition metal complexes , 2006 .

[9]  S. Kovalenko,et al.  Ultrafast solvation of N-methyl-6-quinolone probes local IR spectrum. , 2005, Angewandte Chemie.

[10]  J. Owrutsky,et al.  Vibrational spectroscopy and dynamics of small anions in ionic liquid solutions. , 2005, The Journal of chemical physics.

[11]  J. Owrutsky,et al.  Reorientation and vibrational energy relaxation of pseudohalide ions confined in reverse micelle water pools , 2003 .

[12]  J. McCusker Femtosecond absorption spectroscopy of transition metal charge-transfer complexes. , 2003, Accounts of chemical research.

[13]  Tak W. Kee,et al.  Femtosecond Multicolor Pump−Probe Study of Ultrafast Electron Transfer of [(NH3)5RuIIINCRuII(CN)5]- in Aqueous Solution , 2000 .

[14]  N. Tkachenko,et al.  Laser flash photolysis of IrCl62− in aqueous solutions , 2000 .

[15]  A. Vlček The life and times of excited states of organometallic and coordination compounds , 2000 .

[16]  Helge Lemmetyinen,et al.  Photoinduced Electron Transfer in Phytochlorin-(60)Fullerene Dyads , 1999 .

[17]  N. Tkachenko,et al.  Mechanism of Br2·− and Cl2·− radical anions formation upon IrCl62− photoreduction in methanol solutions containing free Br− and Cl− ions , 1998 .

[18]  N. Tkachenko,et al.  PHOTOREDUCTION OF IRCL62- COMPLEX IN ALCOHOL SOLUTIONS AND ITS REACTION WITH HYDROXYALKYL RADICALS , 1998 .

[19]  V. Plyusnin,et al.  Photochemistry of the IrCl2−6 complex in methanol matrices , 1997 .

[20]  M. Maroncelli,et al.  Nonreactive Dynamics in Solution: The Emerging Molecular View of Solvation Dynamics and Vibrational Relaxation , 1996 .

[21]  M. Maroncelli,et al.  Subpicosecond Measurements of Polar Solvation Dynamics: Coumarin 153 Revisited , 1995 .

[22]  N. I. Sorokin,et al.  Photochemistry of IrCl62− complex in alcohol solutions , 1995 .

[23]  P. Barbara,et al.  Electronic Coherence, Vibrational Coherence, and Solvent Degrees of Freedom in the Femtosecond Spectroscopy of Mixed-Valence Metal Dimers in H2O and D2O , 1995 .

[24]  R. Hanrahan,et al.  Solar-assisted production of hydrogen and chlorine from hydrochloric acid using hexachloroiridate (III) and (IV) , 1993 .

[25]  A. Goursot,et al.  Experimental and theoretical study of the nascent photoredox behavior of the aqueous hexachloroplatinate(IV) ion , 1987 .

[26]  D. Case,et al.  Relativistic scattered wave calculations of hexachloro‐ and hexabromoiridate (IV) , 1984 .

[27]  H. Gray,et al.  Production of hydrogen by irradiation of metal complexes in aqueous solutions , 1981 .

[28]  S. Fukuzumi,et al.  Charge-transfer photochemistry in the cleavage of alkylmetals by hexachloroiridate(IV). ESR studies of paramagnetic intermediates , 1980 .

[29]  A. Smith,et al.  Chemical and Bacteriological Studies of the Photochemical Reaction Product of Ammonium Hexachloroiridate(IV) 1 , 1970, Proceedings of the Society for Experimental Biology and Medicine. Society for Experimental Biology and Medicine.

[30]  V. Balzani,et al.  Photochemical reactions of hexachloroiridate(IV) Ion , 1970 .

[31]  T. Sleight,et al.  The photochemistry of hexachloroiridate (IV) , 1968 .

[32]  C. S. Garner,et al.  A Thermodynamic and Kinetic Study of Hexachloro and Aquopentachloro Complexes of Iridium(III) in Aqueous Solutions , 1962 .

[33]  C. Jørgensen Electron transfer spectra of hexahalide complexes , 1959 .

[34]  C. S. Garner,et al.  Exchange of Radioiridium between Hexachloroiridate(III) and Hexachloroiridate(IV) Ions1a , 1955 .