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The bimolecular rate constants k T O2 for oxygen (O 2 ( 3 Σ g - )) quenching and the efficiencies f Δ T with which singlet oxygen (O 2 . ( 1 ΔS g )) is thereby produced are reported for a range of substituted naphthalene triplet states in acetonitrile, benzene, and cyclohexane. The magnitudes of k T O2 and f Δ T are inversely correlated, and both parameters exhibit pronounced sensitivity to the oxidation potential (E M OX ) of the naphthalene derivative and some dependence on the solvent

Nanosecond laser photolysis measurements of sensitized phosphorescence from oxygen have been used to obtain values for singlet oxygen formation efficiencies during oxygen quenching of excited singlet and triplet states of anthracene and naphthalene derivatives. Oxygen quenching of excited singlet states of anthracene and dicyanoanthracene in cyclohexane has been shown to lead to catalysed production of triplet states with unit efficiency in both cases, but concurrent production of singlet oxygen only occurs in the case of 9,10-dicyanoanthracene with efficiency close to unity whereas the efficiency for singlet oxygen production due to direct oxygen quenching of excited singlet anthracene is close to zero. In contrast to these results, oxygen quenching of the triplet states of anthracene and dicyanoanthracene in cyclohexane yields singlet oxygen with unit efficiency whereas the singlet oxygen formation efficiency during oxygen quenching of triplet 1-ethylnaphthalene is only 0.86 in cyclohexane and drops to 0.51 in acetonitrile. This solvent dependence demonstrates the role which charge transfer interactions play in determining singlet oxygen yields. Further information concerning the decay of excited oxygen-aromatic hydrocarbon charge-transfer complexes have been obtained from picosecond laser pump-probe studies where direct excitation is into the charge-transfer bands of oxygenated 1-ethylnaphthalene. Following the excitation of the charge-transfer complex, the triplet state of 1-ethylnaphthalene is rapidly produced with an efficiency which shows a marked solvent dependency, being 0.4 and 0.8 in acetonitrile and cyclohexane, respectively. The measured yields of singlet oxygen formation following excitation into 1-ethylnaphthalene-oxygen charge-transfer complexes are 0.36 and 0.78 in these two solvents which is greater than that expected on the basis of the measured triplet yields. Mechanisms of quenching of excited states by oxygen which explain these results are discussed.

The efficiencies of singlet oxygen production from the first excited singlet and triplet states of a range of substituted anthracenes in cyclohexane are reported. For all of the anthracene derivatives in this solvent, the efficiency ofsinglet oxygen production from the triplet state, f Δ T , is found to be unity. In contrast, however, the efficiency of singlet oxygen production from the first excited singlet state, f Δ S , varies from zero for anthracene to unity for 9, 10-dicyanoanthracene. It is established that the magnitude of f Δ S is determined by the same factors which govern intersystem crossing yields for anthracene derivatives, i.e., the activation energy for intersystem crossing to higher triplet states