The Interaction of Oxygen with Organic Molecules. II. Oxygen Quenching of the Excited States of Adsorbed Aromatic Hydrocarbons

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Quenching of phosphorescence and fluorescence of aromatic hydrocarbons adsorbed on powdered porous glass or silica gel have been examined as a function of oxygen pressure. It has been found that the phosphorescence quenching at low temperature can be explained mostly by assuming that only those aromatic molecules having an oxygen molecule or molecules within an effective interaction radius are nonphosphorescent (static quenching model). The fluorescence quenching occurs only at much higher oxygen pressures and it has been proposed that contact pairs between aromatic and oxygen molecules, which have shorter intermolecular distances compared to the distances effective for the phosphorescence quenching and give rise to the charge-transfer absorption bands, are relevant. It has been observed that the excimer fluorescence of naphthalene appearing at a higher sample concentration is more strongly affected by oxygen than the monomer fluorescence. The emission spectra from naphthalene-porous glass adsorbate immersed in liquid oxygen and nitrogen have also been examined. The formation of the singlet oxygen (1Δg or 1Σg+) through the interaction of oxygen with triplet molecules has been confirmed by use of the peroxidation reaction of adsorbed anthracene.
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