A series of perylene-3,4,9,10-bis(dicarboximide) (PDI) dimers linked through the bay regions was systematically synthesized to examine the electronic structures and photophysical properties in dependence on the distance and orientation between the two PDI units. The spectroscopic and electrochemical measurements suggested that the coupling value of a directly linked PDI dimer (PDI)2is much larger than those of para- and meta-phenylene-bridged PDI dimers p-(PDI)2and m-(PDI)2. The width of Davydov splitting was quantitatively evaluated to compare the coupling values between the two PDI units in these dimers by absorption spectroscopy in frozen 2-methyl-THF. Excimer formation of PDI dimers induced the strong fluorescence quenching and large red-shifts. Femtosecond transient absorption revealed a broad absorption derived from an excimer in the range from about 600 nm to the near-IR region. The rate constants of formation and decay of the excimer are strongly dependent on the coupling values. Time-resolved measurements on ferrocene-linked p-(PDI)2revealed a competition between the photoinduced processes of electron transfer and excimer formation in PhCN, which is in sharp contrast with the sole electron-transfer process in toluene.
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