Kinetic Measurements of Singlet Oxygen Phosphorescence in Hydrogen-Free Solvents by Time-Resolved Photon Counting.

Solvents lacking hydrogen atoms are very convenient models for elucidating the properties of singlet oxygen, since the lifetime of singlet oxygen in these solvents reaches tens milliseconds. Measuring intrinsic infrared (IR) phosphorescence of singlet oxygen at 1270 nm is the most reliable method of singlet oxygen detection. However, efficient application of the phosphorescence method to these models requires an equipment allowing reliable measurement of the phosphorescence kinetic parameters in the millisecond time range at low rates of singlet oxygen generation, which is a technically difficult problem. Here, we describe a highly sensitive LED (laser) spectrometer recently constructed in our laboratory for the steady-state and time-resolved measurements of the millisecond phosphorescence of singlet oxygen. In the steady-state mode, this spectrometer allows detection of singlet oxygen phosphorescence upon direct excitation of oxygen molecules in the region of dark-red absorption bands at 690 and 765 nm. For kinetic measurements, we used phenalenone as a photosensitizer, microsecond pulses of violet (405 nm) LED for excitation (irradiance intensity, ≤50 μW/cm), a photomultiplier and a computer multichannel scaler for time-resolved photon counting. The decays of singlet oxygen in air-saturated CCl4, CF, and Freon 113 and quenching of singlet oxygen by phenalenone and dissolved molecules of triplet oxygen were measured. The relative values of the radiative rate constants of singlet oxygen in these media were determined. The results were compared with the absorption coefficients of oxygen measured by our group using the methods of laser photochemistry. Critical discussion of the obtained results and the data of other researchers is presented.