Issue 18, 2012

Photophysics of the galvinoxyl free radical revisited

Abstract

The photophysical properties of the free neutral radical galvinoxyl were studied by a combination of femtosecond time-resolved spectroscopy and quantum chemical calculations. The electronic absorption spectrum is dominated by an intense band at 430 nm that is ascribed to the D9,10 ← D0 transitions. Upon photoexcitation at 400 nm, the population of the D9,10 states decays within less than 200 fs to the electronic ground state. This ultrafast internal conversion does not involve intramolecular modes with large amplitude motion as the measured dynamics does not show any significant dependence on the environment, but is most probably facilitated by a high density of electronic states of different character. Depending on the solvent, a weak transient band due to the galvinoxylate anion is also observed. This closed-shell species, which is fluorescent although its deactivation is also dominated by non-radiative decay, is generated upon biphotonic ionization of the solvent and electron capture. The ultrashort excited-state lifetime of the galvinoxyl radical precludes photoinduced disproportionation previously claimed to be at the origin of the formation of both anion and cation.

Graphical abstract: Photophysics of the galvinoxyl free radical revisited

Supplementary files

Article information

Article type
Paper
Submitted
14 Nov 2011
Accepted
06 Jan 2012
First published
06 Jan 2012

Phys. Chem. Chem. Phys., 2012,14, 6352-6358

Photophysics of the galvinoxyl free radical revisited

J. Grilj, C. Zonca, L. M. L. Daku and E. Vauthey, Phys. Chem. Chem. Phys., 2012, 14, 6352 DOI: 10.1039/C2CP23577C

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