Details

Autor(en) / Beteiligte

• Berberich, Martin
• Natali, Mirco
• Spenst, Peter
• Chiorboli, Claudio
• Scandola, Franco
• Würthner, Frank

Titel

Nondestructive Photoluminescence Read-Out by Intramolecular Electron Transfer in a Perylene Bisimide-Diarylethene Dyad

Ist Teil von

• Chemistry : a European journal, 2012-10, Vol.18 (43), p.13651-13664

Ort / Verlag

Weinheim: WILEY-VCH Verlag

Erscheinungsjahr

2012

Link zum Volltext

Quelle

Wiley Online Library Journals Frontfile Complete

Beschreibungen/Notizen

• 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. Tuning fluorescence: A novel, highly stable, photochromic dyad based on a perylene bisimide fluorophore and a diarylethene photochrome was synthesized and its optical and photophysical properties were studied in detail by steady‐state and time‐resolved ultrafast spectroscopy (see figure; o=open form, c= closed form). Solvent‐dependent fluorescence studies revealed that the emission of the ring‐closed form is drastically quenched in solvents of medium‐to‐high polarities.