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Excited-State Dynamics of an Environment-Sensitive Push–Pull Diketopyrrolopyrrole: Major Differences between the Bulk Solution Phase and the Dodecane/Water Interface

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journal contribution
posted on 21.08.2014, 00:00 by Sabine Richert, Sandra Mosquera Vazquez, Marek Grzybowski, Daniel T. Gryko, Alexander Kyrychenko, Eric Vauthey
The excited-state dynamics of a diketopyrrolopyrrole (DPP) derivative with push–pull substituents has been investigated in a variety of solvents and at the dodecane/water and dodecane/heavy-water interfaces using a combination of ultrafast spectroscopic techniques, including transient electronic absorption and time-resolved surface second-harmonic generation. Whereas the photophysics of a nonpolar DPP analogue is mostly independent of the solvent, the fluorescence decay of the push–pull DPP accelerates strongly by going from aprotic to protic solvents. As this effect increases with the polarity and the hydrogen-bond-donating ability of the solvent, it is attributed to the occurrence of H-bond-assisted nonradiative deactivation induced by the charge-transfer character of the excited state that favors the coupling of the molecule to the H-bond network of the solvent. At the dodecane/water interface, the excited-state lifetime is longer by a factor of ca. 20 than that estimated in pure water and increases further by a factor of about 3 when going to the dodecane/heavy-water interface. This isotope effect, that is more than twice as strong as that measured in bulk solutions, and molecular dynamic simulations indicate that the slowing down of the dynamics at the interface cannot be solely ascribed to a reduced accessibility of the DPP molecule to the aqueous phase. The slower excited-state decay is rather assigned to the conjunction of several effects, such as the strengthening of the H-bond network formed by the interfacial water molecules and the lower local polarity of the interfacial region.