Get access

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

Authors

  • Martin Berberich,

    1. Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84756
    Search for more papers by this author
  • Mirco Natali,

    1. Università di Ferrara, Dipartimento di Chimica, Via L. Borsari 46, 44100 Ferrara (Italy), Fax: (+39) 0532-240-709
    Search for more papers by this author
  • Peter Spenst,

    1. Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84756
    Search for more papers by this author
  • Dr. Claudio Chiorboli,

    1. ISOF-CNR, Sezione di Ferrara, Via L. Borsari 46, 44100 Ferrara (Italy)
    Search for more papers by this author
  • Prof. Dr. Franco Scandola,

    Corresponding author
    1. Università di Ferrara, Dipartimento di Chimica, Via L. Borsari 46, 44100 Ferrara (Italy), Fax: (+39) 0532-240-709
    • Università di Ferrara, Dipartimento di Chimica, Via L. Borsari 46, 44100 Ferrara (Italy), Fax: (+39) 0532-240-709
    Search for more papers by this author
  • Prof. Dr. Frank Würthner

    Corresponding author
    1. Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84756
    • Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84756
    Search for more papers by this author

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.

Ancillary