title: Fluorescence photoswitching and photoreversible two-way energy transfer in a photochrome-fluorophore dyad.
abstract: A thorough photophysical study of a photochrome-fluorophore dyad (3), combining a fluorescent laser dye (DCM-type, , Φ(1) = 0.27) and a photochromic diarylethene (2), obtained by click chemistry, is presented. In addition to photochromism, the open form (OF) of 2 exhibits fluorescence (Φ(-OF) = 0.016), whereas the closed form (CF) does not. Fluorescence is switched upon alternate UV/visible irradiation of 2. The emission band of 2-OF matches the absorption band of 1 (400-550 nm), whereas the emission band of 1 overlaps the absorption band of 2-CF (550-700 nm). Therefore, a photoreversible two-way excitation energy transfer (EET), controlled by the state of the photochromic moiety, is obtained in the dyad 3. Their efficiencies are quantified as Φ(EET)(OF→F) = 85% and as Φ(EET)(F→CF) ~ 100% from the comparison of emission and excitation spectra between 1, 2, and 3. These results are fully compatible with the shortening of fluorescence lifetimes (from τ(-OF) = 70 ps and 170 ps essentially to τ(-OF) < 10 ps) and to the values of Förster radii determined for 3 (R(0)(OF → F) = 29 Å and R(0)(F → CF) = 71 Å), evidencing a Förster-type resonance energy transfer mechanism (FRET). An important outcome of this two-way FRET is the possibility to quench 49% of the fluorescence in 3 at PSS upon UV irradiation, corresponding to the conversion extent of the photochromic reaction, which is different from 2 (α(CF) = 91%). This is a clear example of a situation where the presence of FRET between the photochromic unit and the fluorophore affects noticeably the photochromic properties of the dyad molecule 3.
authors.affiliation: PPSM, ENS Cachan, CNRS, UMR8531, 61 av. Président Wilson, F-94235 Cachan cedex, France.
authors.forename: Karima
authors.initials: K
authors.lastname: Ouhenia-Ouadahi
authors.forename: Rémi
authors.initials: R
authors.lastname: Métivier
authors.forename: Stéphane
authors.initials: S
authors.lastname: Maisonneuve
authors.forename: Aurélie
authors.initials: A
authors.lastname: Jacquart
authors.forename: Juan
authors.initials: J
authors.lastname: Xie
authors.forename: Anne
authors.initials: A
authors.lastname: Léaustic
authors.forename: Pei
authors.initials: P
authors.lastname: Yu
authors.forename: Keitaro
authors.initials: K
authors.lastname: Nakatani