Pure and Applied Chemistry

Abstract: Experimental investigations of photoinduced charge transport in synthetic DNA capped hairpins possessing electron acceptor and donor stilbene chromophores at either end have established the mechanism, dynamics, and efficiency of charge transport in DNA. The mechanism for charge transport in repeating A-T base pairs (A-tracts) was found to change from single-step superexchange at short distances to multistep incoherent hole hopping at longer distances. The rate constants for base-to-base hole hopping in longer A- and G‑tract sequences are 1.2 × 10⁹ s^–1 and 4.3 × 10⁹ s^–1, respectively, considerably slower than the rate constants associated with molecular wires. Even slower rate constants are observed for alternating or random base sequences such as those encountered in natural DNA. The efficiency of charge separation in capped hairpins with A-tract sequences is also low as a consequence of the competition of hole hopping with charge recombination. Significantly higher efficiencies for charge separation are possible using diblock purine base sequences consisting of two or three adenines followed by a larger number of guanines. The short A-block serves as a molecular rectifier, slowing down charge recombination. More efficient charge separation can also be achieved using non-natural bases or by using the triplet acceptor anthraquinone for hole injection.