Nitroxyl free radical enhancement of the forbidden O2(3Σ- g) ← O2(1Δg) radiative transition in chlorinated hydrocarbon solvents

R. E. Belford, G. Seely, John Devens Gust, Thomas A Moore, Ana L Moore, N. J. Cherepy, S. Ekbundit, J. E. Lewis, S. H. Lin

Research output: Contribution to journalArticle

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Abstract

Utilizing transient near-IR luminescence spectroscopy, we have shown that free radicals like TEMPO (2,2,6,6- tetramethylpiperidine-N-oxyl) increase the rate of the forbidden radiative transition of singlet oxygen in chlorinated hydrocarbon solvents. The quantum yield for emission has been shown to depend on the nature of the substituent group in the 4′ position. Concomitant with this effect is a slight high energy shift in the steady state singlet oxygen phosphorescence spectrum. Additional experiments with TEMP (2,2,6,6-tetramethylpiperidine) have shown that the nitroxyl group is necessary for this effect. Using the kinetic equations associated with a collision complex model, we have investigated a curve crossing (isophotic) point observed in the 1270 nm luminescence decays at various TEMPO concentrations. This information indicates that we are observing a contact complex characterized by a weak interaction energy and a short lifetime. We have also determined the conditions under which the isophotic point can be observed.

Original languageEnglish
Pages (from-to)125-133
Number of pages9
JournalJournal of Photochemistry and Photobiology A: Chemistry
Volume70
Issue number2
DOIs
Publication statusPublished - Feb 15 1993

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Chlorinated Hydrocarbons
Singlet Oxygen
Electron transitions
Free radicals
free radicals
Free Radicals
Luminescence
weak energy interactions
hydrocarbons
luminescence
Phosphorescence
Oxygen
augmentation
Quantum yield
oxygen
phosphorescence
kinetic equations
Spectroscopy
life (durability)
Kinetics

ASJC Scopus subject areas

  • Bioengineering
  • Physical and Theoretical Chemistry

Cite this

Nitroxyl free radical enhancement of the forbidden O2(3Σ- g) ← O2(1Δg) radiative transition in chlorinated hydrocarbon solvents. / Belford, R. E.; Seely, G.; Gust, John Devens; Moore, Thomas A; Moore, Ana L; Cherepy, N. J.; Ekbundit, S.; Lewis, J. E.; Lin, S. H.

In: Journal of Photochemistry and Photobiology A: Chemistry, Vol. 70, No. 2, 15.02.1993, p. 125-133.

Research output: Contribution to journalArticle

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AU - Seely, G.

AU - Gust, John Devens

AU - Moore, Thomas A

AU - Moore, Ana L

AU - Cherepy, N. J.

AU - Ekbundit, S.

AU - Lewis, J. E.

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AB - Utilizing transient near-IR luminescence spectroscopy, we have shown that free radicals like TEMPO (2,2,6,6- tetramethylpiperidine-N-oxyl) increase the rate of the forbidden radiative transition of singlet oxygen in chlorinated hydrocarbon solvents. The quantum yield for emission has been shown to depend on the nature of the substituent group in the 4′ position. Concomitant with this effect is a slight high energy shift in the steady state singlet oxygen phosphorescence spectrum. Additional experiments with TEMP (2,2,6,6-tetramethylpiperidine) have shown that the nitroxyl group is necessary for this effect. Using the kinetic equations associated with a collision complex model, we have investigated a curve crossing (isophotic) point observed in the 1270 nm luminescence decays at various TEMPO concentrations. This information indicates that we are observing a contact complex characterized by a weak interaction energy and a short lifetime. We have also determined the conditions under which the isophotic point can be observed.

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