Helical aromatic oligoamide foldamers as organizational scaffolds for photoinduced charge transfer

Martin Wolffs, Nicolas Delsuc, Dirk Veldman, Vân Anh Nguyên, René M Williams, Stefan C J Meskers, René A J Janssen, Ivan Huc, Albertus P H J Schenning
Journal of the American Chemical Society 2009 April 8, 131 (13): 4819-29
Here we report the synthesis and characterization of four quinoline-derived foldamers with increasing oligomeric length; dimer O2P, tetramer O4P, pentamer O5P, and nonamer O9P functionalized with on one end an oligo(p-phenylene vinylene) (OPV) and on the other end a perylene bisimide (PB) chromophore. (1)H NMR confirms the formation of the expected folded structures in both toluene and chloroform solution. The structural predictability and rigidity of the oligomeric series enabled us to investigate the effect of a helical bridge and chromophore position on the photoinduced processes in the electron OPV-PB donor-acceptor pair in chloroform and toluene. The helical properties of the bridge ensured that the chromophore separation distance through space is different from the separation distance through the bridge. For all foldamer-solvent combinations studied, excitation of either OPV or PB results in nearly quantitative quenching of the fluorescence indicating a fast charge separation reaction between the OPV and PB. Femtosecond photoinduced absorption measurements confirmed the fast formation of a charge-separated state. The recombination reaction involves a combination of direct decay to the ground state and the formation of an intermediate triplet state, with their balance depending on the foldamer-solvent combination. Molecular orbital calculations rationalize the fast photoinduced charge separation, by revealing that the bridging foldamer mediates the charge transfer from donor to acceptor via the superexchange mechanism. Remarkably low attenuation factors (beta(CS) approximately 10(-2) A(-1)) were obtained using either through space or through bridge separation distance. However, in these calculations only three of the four foldamers show the expected linear behavior between the logarithm of the charge separation rate constant and the distance between the chromophores. The combined results show when a helical bridge is separating the charge transfer couple, hampering the usefulness of a uniform description of the charge-separation phenomena.

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