Porphyrins: XII. Luminescence of copper complexes at liquid nitrogen temperature

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Abstract

Luminescence spectra, excitation spectra, lifetimes, and quantum yields at liquid nitrogen temperature in various solvents are reported for several copper porphyrins in an attempt to understand the nature of the luminescent state. From excitation spectra a natural radiative lifetime of the luminescent “tripdoublet” state is estimated at ∼70 μsec for Cu octalkylporphin, with observed lifetimes from 60–80 μsec, and yields ∼0.6. Both CuTPP and CuP show nonexponential decay curves. The decay curve for CuTPP can be fitted with three lifetimes (∼600 μsec, ∼150 μsec, ∼25 μsec) while CuP can be fitted with two time (∼750 μsec, ∼150 μsec). The CuEtio luminescence is shown to persist weakly at room temperature. Some effects of solvent on the spectra are discussed: In particular the complexing effect of organic bases and the band sharpening in certain n-paraffins.

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