Fast intramolecular charge transfer with a planar rigidized electron donor/acceptor molecule

Journal of the American Chemical Society
Toshitada YoshiharaKlaas A Zachariasse

Abstract

The planar rigidized molecule fluorazene (FPP) undergoes fast reversible intramolecular charge transfer (ICT) in the excited state, with a reaction time of 12 ps in the polar solvent ethyl cyanide at -45 degrees C. The ICT state of FPP has a dipole moment mu(e)(ICT) of 13 D, much larger than that of the locally excited state LE (1 D). The ICT behavior of FPP is similar to that of its flexible counterpart N-phenylpyrrole (PP), for which mu(e)(ICT) = 12 D. These results show that intramolecular charge transfer to a planar ICT state can occur efficiently. In designing ICT systems capable of rapid switching, it is therefore important to realize that large amplitude motions such as those necessary for the formation of a twisted intramolecular charge transfer (TICT) state are not required.

References

Apr 26, 2003·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Toshitada YoshiharaKlaas A Zachariasse
Jan 30, 2004·Journal of the American Chemical Society·Dmitrij Rappoport, Filipp Furche
Feb 12, 2004·Journal of the American Chemical Society·Klaas A ZachariasseReinhard Machinek

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