Abstract
The photochemistry of bisimide II has been studied in solution by conventional means as well as by time-resolved laser techniques. Compound II, the adduct of benzophenonetetracarboxylic dianhydride and 2 equivalents of 2-isopropylaniline, was designed as a model for inherently photosensitive, solvent-soluble polyimides — whose photochemistry is not well understood. A low temperature phosphorescence spectrum of matrix-isolated II, along with other results, indicates that the reactivity of II following photon absorption (300 – 365 nm) is due to its lowest n,π * triplet state. Triplet II behaves in a similar fashion to triplet benzophenone, being efficiently quenched by 1,3-dienes and photoreduced by compounds containing labile CH bonds. The absorption spectrum of the intermediate ketyl in the photoreduction was observed, and phosphorescence quenching rate constants for excited II determined in the presence of 2-propanol or triethylamine. The equation for determining quenching rate constants in a “gated” quenching experiment was derived and differs from that used in normal Stern-Volmer studies.
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