Solvent Mediated Intramolecular Photoinduced Electron Transfer in a Fluorene-Perylene Bisimide Derivative

Photoinduced electron transfer from fluorene to perylene bisimide has been studied for 2,7-bis(N-(1-hexylheptyl)-3,4:9,10-perylene-bisimide-N'-yl))-9,9-didodecylfluorene (PFP) in 11 different organic solvents. The intramolecular charge-separated state in PFP is almost isoenergetic with the locally excited state of the perylene bisimide. As a consequence of the small change in free energy for charge separation, the electron transfer rate strongly depends on subtle changes in the medium. The rate constant k_CS for the electron transfer from fluorene to perylene bisimide moiety in the excited state varies over more than 2 orders of magnitude (∼10⁸−10¹⁰ s^-1) with the solvent but does not show the familiar increase with polarity. The widely differing rate constants can be successfully explained by considering (1) the contribution of the polarization energy of the dipole moment in the transition state and by (2) the classical Marcus-Jortner model and assuming a spherical cavity for the charge-separated state. Using the first model, we show that lnk_CS should vary linearly with Δf [Δf = (ε_r − 1)/(2ε_r + 1) − (n² − 1)/(2n² + 1), where ε_r and n represent the static dielectric constant and the refractive index of the solvent, respectively], in accordance with experimental results. The second model, where the reorganization energy scales linearly with Δf, provides quantitative agreement with experimental rate constants within a factor of 2.