Ultrafast Charge Transfer Dynamics in a Slip-Stacked Donor–Acceptor–Acceptor System

Photoexcitation of molecular electron donor and/or acceptor chromophore aggregates can greatly affect their charge-transfer dynamics. Excitonic coupling not only alters the energy landscape in the excited state but may also open new photophysical pathways, such as symmetry-breaking charge separation (SB-CS). Here, we investigate the impact of excitonic coupling on a covalent donor–acceptor–acceptor system comprising a perylene donor (Per) and two perylenediimide (PDI) acceptor chromophores in which the three components are π-stacked in a geometry that is slipped along their long axes (Per-PDI 2 ). Following selective photoexcitation of PDI, femtosecond transient absorption data for Per-PDI 2 is compared to that for the single-donor, single-acceptor Per-PDI system, and the PDI 2 dimer, which both have the same interchromophore geometry as Per-PDI 2 . The data show that electron transfer from Per to the lower exciton state of the PDI dimer is slower than that of the single PDI acceptor system. This is due to the lower free energy of the reaction for charge separation because of the electronic stabilization afforded by the excitonic coupling between the PDIs. While PDI 2 was shown previously to undergo ultrafast SB-CS, the strong π–π electronic interaction of Per with the adjacent PDI in Per-PDI 2 breaks the electronic symmetry of the PDI dimer, resulting in the oxidation of Per rather than SB-CS. These results show that the electronic coupling between molecules designed to accept charges produced by SB-CS in molecular dimers and the chromophores comprising the dimer must be balanced to favor SB-CS.