Ultrafast Twisting of the Indoline Donor Unit Utilized in Solar Cell Dyes: Experimental and Theoretical Studies
Previous time-resolved measurements on D149, the most-studied dye of the indoline family, had shown a fast time-component of 20–40 ps that had tentatively been attributed to structural relaxation. Using femtosecond transient absorption, we have investigated the isolated indoline donor unit (i.e., without acceptor group) and found an ultrafast decay characterized by two lifetimes of 3.5 and 23 ps. Density functional theory calculations show π-bonding and π*-antibonding character of the central ethylene group for the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), respectively. The LUMO is localized on the flexible vinyl-diphenyl region of the donor unit and a twist…
The Role of Site-Specific Hydrogen Bonding Interactions in the Solvation Dynamics of N-Acetyltryptophanamide
Measurements of the ultrafast broadband UV fluorescence of N-acetyltryptophanamide (NATA) provide detailed information on its relaxation patterns in three different solvents: methanol (MeOH), water and acetonitrile (ACN). Several processes leading to excited state solvation and cooling are found to occur on different characteristic time scales and are thoroughly analyzed. Comparison between protic MeOH and aprotic ACN allows one to single out a 12 Ps component in the former, which is attributed to the rearrangement of H-bonds existing between the protic solvent and excited NATA. This significantly stabilizes the excited state and provides the molecule with an efficient cooling mechanism. Th…
Polychromatic femtosecond fluorescence studies of metal–polypyridine complexes in solution
Femtosecond-resolved broadband fluorescence studies are reported for[ M(bpy)(3)](2+) (M = Fe, Ru), RuN3 and RuN719 complexes in solution. We investigated the pump wavelength dependence of the fluorescence of aqueous [ Fe(bpy)(3)](2+) and the solvent and ligand dependence of the fluorescence of Ru-complexes excited at 400 nm. For all complexes, the (MLCT)-M-1 fluorescence appears at zero time delay with a mirror-like image with respect to the absorption. It decays in <= 30-45 fs due to intersystem crossing to the (MLCT)-M-3 states, but a longer lived component of similar to 190 fs additionally shows up in RuN719 and RuN3. No solvent effects are detected. The very early dynamics are character…