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

Bradley, Jillian M.; Coleman, Adam F.; Brown, Paige J.; Huang, Yuheng; Young, Ryan M.; Wasielewski, Michael R.

doi:10.1073/pnas.2313575120

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

Journal Article · Mon Nov 20 00:00:00 EST 2023 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2313575120· OSTI ID:2217252

Bradley, Jillian M. ^[1]; Coleman, Adam F. ^[1]; Brown, Paige J. ^[1]; Huang, Yuheng ^[1];

^[1];

^[1]

Department of Chemistry, Northwestern University, Evanston, IL 60208-3113, Paula M. Trienens Institute for Sustainability and Energy, Northwestern University, Evanston, IL 60208-3113

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 (S ₁ ) 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 ( m PDI ₂ ) covalently linked to a secondary electron donor, peri -xanthenoxanthene (PXX) and a secondary electron acceptor, partially fluorinated naphthalenediimide (FNDI). Upon selective photoexcitation of m PDI ₂ , transient absorption spectroscopy shows that m PDI ₂ undergoes SB-CS, followed by two secondary charge transfer reactions to generate a PXX ^•+ - m PDI ₂ -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.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-99ER14999

OSTI ID:: 2217252

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 120 Journal Issue: 48; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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