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The fluorescence emission intensities in a variety of solvents with different polarities and electrochemical studies revealed that there was electron transfer from EtP5 to the DIBDP units, and the electron-transfer process had influence on the fluorescence emission but not on the triplet states of DIBDP moieties in EtP5-DIBDP, which verified the results of density functional theory calculations. The triplet state lifetimes of EtP5-DIBDP were longer than those of DIBDP and G and the photooxidation abilities of EtP5-DIBDP were better than