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

✍ Scribed by R.E. Belford; G. Seely; D. Gust; T.A. Moore; A. Moore; N.J. Cherepy; S. Ekbundit; J.E. Lewis; S.H. Lin

Publisher
Elsevier Science
Year
1993
Tongue
English
Weight
902 KB
Volume
70
Category
Article
ISSN
1010-6030

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✦ Synopsis

Utilizing transient near-IR luminescence spectroscopy, we have shown that free radicals like TEMPO (2,2,6, 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 TE%fP (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 wntact 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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