Substitution Effects of C-C Triple Bonds on Deactivation Processes from the Fluorescent State of Pyrene Studied by Emission and Transient Absorption Measurements

الملخص EN

Pyrenes substituted with tert-butylethynyl, trimethylsilylethynyl, and trimethylsilylbutadiynyl groups were prepared, and the fluorescence yields (Φf), lifetimes, and triplet-triplet absorption were measured in cyclohexane.

Upon introduction of the groups possessing triple bond(s) to the pyrene skeleton, the fluorescence rate (kf) increased.

The variation of the terminating groups did not appreciably affect the Φf and kf values.

Increasing the number of the triple bond, the kf values increased by the magnitude of order whereas the Φf were not varied.

The effect of the ethynyl groups on the kf values was rationalized by the Strickler-Berg equation considering an increase of the 1La transition moment.

Triplet-triplet absorption spectra of pyrene derivatives were obtained.

The intersystem crossing rates (kisc) increased upon increasing the number of triple bonds terminated with the trimethylsilyl group whereas those between ethynylpyrenes were independent of the terminating groups.

Heavy atom effect failed to rationalize the enhancement of the kisc values upon adding the triple bond to the pyrene moiety.