Solvent-controlled electron transfer in crystal violet lactone

Xiang Li, Mark Maroncelli

Research output: Contribution to journalArticle

14 Citations (Scopus)

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.

Original languageEnglish (US)
Pages (from-to)3746-3754
Number of pages9
JournalJournal of Physical Chemistry A
Volume115
Issue number16
DOIs
StatePublished - Apr 28 2011

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electron transfer
Electrons
crystals
Charge transfer
charge transfer
Excited states
crystal violet lactone
Solvation
Dipole moment
Free energy
excitation
Reaction rates
solvation
Rate constants
polarity
reaction kinetics
dipole moments
friction
free energy
Friction

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

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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.",
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Solvent-controlled electron transfer in crystal violet lactone. / Li, Xiang; Maroncelli, Mark.

In: Journal of Physical Chemistry A, Vol. 115, No. 16, 28.04.2011, p. 3746-3754.

Research output: Contribution to journalArticle

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