title: Nondestructive photoluminescence read-out by intramolecular electron transfer in a perylene bisimide-diarylethene dyad.
abstract: 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.
authors.affiliation: Universität Würzburg, Institut für Organische Chemie, Center for Nanosystems Chemistry, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Berberich
authors.forename: Mirco
authors.initials: M
authors.lastname: Natali
authors.forename: Peter
authors.initials: P
authors.lastname: Spenst
authors.forename: Claudio
authors.initials: C
authors.lastname: Chiorboli
authors.forename: Franco
authors.initials: F
authors.lastname: Scandola
authors.forename: Frank
authors.initials: F
authors.lastname: Würthner