期刊
出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.2026462118
关键词
charge transfer; hydrogen bonding; corrole; folding; perylene diimide
资金
- National Science Centre, Poland [HARMONIA 2016/22/M/ST5/00431, PRELUDIUM 2016/23/N/ST5/00052]
- NSF [CHE 1800602]
- National Science Centre [2017/25/B/ST5/01011]
- Wroclaw Centre for Networking and Supercomputing [299]
- National Institute of Diabetes and Digestive and Kidney Diseases of the NIH [R01DK019038]
- NSF (MPS AGEP-GRS)
This study elucidates the factors controlling charge transfer rates in relatively flexible conjugates and identifies a scorpion-shaped molecular architecture that promotes high-speed electron transfer and hole transfer. These findings are crucial for guiding the construction of effective donor-acceptor assemblies and understanding energy flows in biological systems.
Elucidating the factors that control charge transfer rates in relatively flexible conjugates is of importance for understanding energy flows in biology as well as assisting the design and construction of electronic devices. Here, we report ultrafast electron transfer (ET) and hole transfer (HT) between a corrole (Cor) donor linked to a perylene-diimide (PDI) acceptor by a tetrameric alanine (Ala)(4). Selective photoexcitation of the donor and acceptor triggers subpicosecond and picosecond ET and HT. Replacement of the (Ala)(4) linker with either a single alanine or phenylalanine does not substantially affect the ET and HT kinetics. We infer that electronic coupling in these reactions is not mediated by tetrapeptide backbone nor by direct donor-acceptor interactions. Employing a combination of NMR, circular dichroism, and computational studies, we show that intramolecular hydrogen bonding brings the donor and the acceptor into proximity in a scorpion-shaped molecular architecture, thereby accounting for the unusually high ET and HT rates. Photoinduced charge transfer relies on a (Cor)NH center dot center dot center dot O=C-NH center dot center dot center dot O=C(PDI) electronic-coupling pathway involving two pivotal hydrogen bonds and a central amide group as a mediator. Our work provides guidelines for construction of effective donor-acceptor assemblies linked by long flexible bridges as well as insights into structural motifs for mediating ET and HT in proteins.
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