title: Can the Excited State Energy of a Pyrenyl Unit Be Directly Transferred to a Perylene Bisimide Moiety?
abstract: A pyrenyl unit (Py) was chemically connected to a perylene bisimide (PBI) moiety through a long and flexible linker, 4,7,10-trioxa-1,13-tridecanediamine (TOA), resulting in a fluorescent dyad, PBI-TOA-Py. Ultraviolet-visible absorption and fluorescence studies revealed that the two fluorescent units of PBI-TOA-Py behave independently. However, efficient Förster resonance energy transfer (FRET) from the Py unit to the PBI moiety in solution state was also observed. Temperature and solvent effect studies demonstrated that the energy transfer efficiency is highly dependent upon solution temperature and solvent nature. Specifically, for the dimethylformamide (DMF) solution of PBI-TOA-Py, the FRET efficiency is close to 88% at temperatures below ∼40 °C, but the efficiency greatly decreases to nearly zero when the temperature exceeds ∼80 °C. Moreover, addition of HAc into the DMF solution at room temperature could reduce the energy transfer efficiency to nearly zero, suggesting that the excited state energy of Py cannot be directly transferred to the PBI structure even though they are properly and chemically bonded. On the basis of the observations and time-resolved studies, it is believed that the observed efficient FRET from the Py unit to the PBI moiety occurs mainly through Py excimer formation, which could be a result of intermolecular association of the compound. Thus, the applications of the fluorescent dyad in solvent discrimination and trace water determination in organic solvents were verified through example studies.
authors: Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), School of Chemistry and Chemical Engineering, Shaanxi Normal University , Xi'an 710062, P. R. China.
authors: Gang
authors: G
authors: Wang
authors: Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), School of Chemistry and Chemical Engineering, Shaanxi Normal University , Xi'an 710062, P. R. China.
authors: Congdi
authors: C
authors: Shang
authors: Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), School of Chemistry and Chemical Engineering, Shaanxi Normal University , Xi'an 710062, P. R. China.
authors: Li
authors: L
authors: Wang
authors: Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), School of Chemistry and Chemical Engineering, Shaanxi Normal University , Xi'an 710062, P. R. China.
authors: Haonan
authors: H
authors: Peng
authors: Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), School of Chemistry and Chemical Engineering, Shaanxi Normal University , Xi'an 710062, P. R. China.
authors: Shiwei
authors: S
authors: Yin
authors: Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), School of Chemistry and Chemical Engineering, Shaanxi Normal University , Xi'an 710062, P. R. China.
authors: Yu
authors: Y
authors: Fang