科研之友
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摘要
A novel, highly stable photochromic dyad 3 based on a perylene bisimide (PBI) fluorophore and a diarylethene (DAE) photochrome was synthesized and the optical and photophysical properties of this dyad were studied in detail by steady-state and time-resolved ultrafast spectroscopy. This photochromic dyad can be switched reversibly by UV-light irradiation of its ring-open form 3?o leading to the ring-closed form 3?c, and back reaction of 3?c to 3?o by irradiation with visible light. Solvent-dependent fluorescence studies revealed that the emission of ring-closed form 3?c is drastically quenched in solvents of medium (e.g., chloroform) to high (e.g., acetone) polarities, while the emission of the ring-open form 3?o is appreciably quenched only in highly polar solvents like DMF. The strong fluorescence quenching of 3?c is attributed to a photoinduced electron-transfer (PET) process from the excited PBI unit to ring-closed DAE moiety, as this process is thermodynamically highly favorable with a Gibbs free energy value of -0.34 eV in dichloromethane. The electron-transfer mechanism for the fluorescence quenching of ring-closed 3?c is substantiated by ultrafast transient measurements in dichloromethane and acetone, revealing stabilization of charge-separated states of 3?c in these solvents. Our results reported here show that the new photochromic dyad 3 has potential for nondestructive read-out in write/read/erase fluorescent memory systems.
- 出版日期2012-10
