Harvesting electrons and holes from photodriven symmetry-breaking charge separation within a perylenediimide photosynthetic model dimer.

Understanding how to utilize symmetry-breaking charge separation (SB-CS) offers a path toward increasingly efficient light-harvesting technologies. This process plays a central role in the first step of photosynthesis, in which the dimeric "special pair" of the photosynthetic reaction center enters a coherent SB-CS state after photoexcitation. Previous research on SB-CS in both biological and synthetic chromophore dimers has focused on increasing the efficiency of light-driven processes. In a chromophore dimer undergoing SB-CS, the energy of the radical ion pair product is nearly isoenergetic with that of the lowest excited singlet (S1) state of the dimer. This means that very little energy is lost from the absorbed photon. In principle, the relatively high energy electron and hole generated by SB-CS within the chromophore dimer can each be transferred to adjacent charge acceptors to extend the lifetime of the electron-hole pair, which can increase the efficiency of solar energy conversion. To investigate this possibility, we have designed a bis-perylenediimide cyclophane (mPDI2) covalently linked to a secondary electron donor, peri-xanthenoxanthene (PXX) and a secondary electron acceptor, partially fluorinated naphthalenediimide (FNDI). Upon selective photoexcitation of mPDI2, transient absorption spectroscopy shows that mPDI2 undergoes SB-CS, followed by two secondary charge transfer reactions to generate a PXX•+-mPDI2-FNDI•- radical ion pair having a nearly 3 µs lifetime. This strategy has the potential to increase the efficiency of molecular systems for artificial photosynthesis and photovoltaics.

Direct observation of chirality-induced spin selectivity in electron donor-acceptor molecules.

The role of chirality in determining the spin dynamics of photoinduced electron transfer in donor-acceptor molecules remains an open question. Although chirality-induced spin selectivity (CISS) has been demonstrated in molecules bound to substrates, experimental information about whether this process influences spin dynamics in the molecules themselves is lacking. Here we used time-resolved electron paramagnetic resonance spectroscopy to show that CISS strongly influences the spin dynamics of isolated covalent donor-chiral bridge-acceptor (D-Bχ-A) molecules in which selective photoexcitation of D is followed by two rapid, sequential electron-transfer events to yield D•+-Bχ-A•-. Exploiting this phenomenon affords the possibility of using chiral molecular building blocks to control electron spin states in quantum information applications.