Solvent-controlled electron transfer in crystal violet lactone

J Phys Chem A. 2011 Apr 28;115(16):3746-54. doi: 10.1021/jp106240x. Epub 2010 Sep 10.

Abstract

Steady-state and picosecond time-resolved emission experiments are used to examine the excited-state charge transfer reaction of crystal violet lactone (CVL) in aprotic solvents. Solvatochromic analysis using a dielectric continuum model suggests dipole moments of 9-12 D for the initially excited (LE) state and ∼24 D for the charge-transfer (CT) state. Intensities of steady-state emission as well as kinetic data provide free energies for the LE → CT reaction that range from +12 kJ/mol in nonpolar solvents to -10 kJ/mol in highly polar solvents at 25 °C. Reaction rates constants, which lie in the range of 10-100 ns(-1) in most solvents, depend on both solvent polarity and solvent friction. In highly polar solvents, rates are correlated to solvation times in a manner that indicates that the reaction is a solvent-controlled electron transfer on an adiabatic potential surface having a modest barrier.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Electron Transport
  • Gentian Violet / chemistry*
  • Models, Molecular
  • Molecular Structure
  • Solvents / chemistry
  • Thermodynamics

Substances

  • Solvents
  • Gentian Violet
  • crystal violet lactone