Reactions of excited-state benzophenone ketyl radical in a room-temperature ionic liquid

Phys Chem Chem Phys. 2010 Feb 28;12(8):1963-70. doi: 10.1039/b920131a. Epub 2010 Jan 22.

Abstract

The photochemistry of the benzophenone ketyl radical in D(1) excited state, BPH(D(1)), was studied by means of two-color dual-pulse laser flash photolysis (355 and 532 nm) in a room-temperature ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (Bmim-TFSA), and in methanol. Upon excitation with the 532 nm pulse, BPH(D(1)) emitted strong fluorescence. The transient absorption and fluorescence spectra of BPH(D(1)) were measured with nanosecond and sub-nanosecond time resolution, respectively. The observed Stokes shift was 1700 cm(-1) in Bmim-TFSA, and this shift was close to that in acetonitrile. The fluorescence lifetime of BPH(D(1)) was determined to be 5 ns in Bmim-TFSA, and again the value was close to that in acetonitrile. The rate constant of the reaction of BPH(D(1)) with CCl(4) in Bmim-TFSA was determined to be (2.1 +/- 0.4) x 10(9) M(-1) s(-1), which was 10 times the rate constant calculated on the basis of the bulk viscosity of Bmim-TFSA. The results are discussed in terms of the effective microscopic viscosity of the ionic liquid that was recently reported for the cage effect.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Benzophenones / chemistry*
  • Free Radicals
  • Imidazoles / chemistry
  • Ionic Liquids / chemistry*
  • Photolysis
  • Solvents / chemistry
  • Spectrometry, Fluorescence
  • Temperature
  • Viscosity

Substances

  • 1-butyl-3-methylimidazolium
  • Benzophenones
  • Free Radicals
  • Imidazoles
  • Ionic Liquids
  • Solvents
  • benzophenone