The long-wavelength n.PI.* phosphorescence spectra of p-quinones in polycrystalline solutions at 77K.

概要

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Besides the usual nπ* phosphorescence spectra, broad, long-wavelength nπ* phosphorescence spectra are observed in normal paraffine solutions, such as a heptane solution, of 1,4-naphthoquinone, and in a benzene solution of 5,14 : 7,12-pentacenediquinone at 77 K. The energy difference between the two spectra are ca. 750 and 980 cm−1 respectively. The intensity of the long-wavelength spectra relative to the short-wavelength spectra becomes weaker with decreases in the concentrations of the quinones, and the lifetimes of the long-wavelength spectra are shorter than those of the short-wavelength spectra. These long-wavelength spectra are assigned to those of the quinone aggregates. The excitation spectra of these phosphorescences have also been obtained. An explanation of the above red-shift of the nπ* phosphorescence spectra of the aggregates is presented; in it, the phosphorescence state of the aggregates corresponds to the nπ* triplet excimer state.
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