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Long-range charge transfer pervades biology, chemistry, and engineering, as it is critical for life-sustaining processes, chemical transformations, energy conversion, as well as electronic and photonic technologies (Phys. Chem. Chem. Phys. 2020, 22, 21583-21629). Elucidating the factors that control electron transfer rates is of importance for understanding energy flows in biology as well as assisting the design and construction of electronic devices. In collaboration with the Polish Academy of Sciences and California Institute of Technology, Prof. Vullev’s group discovered ultrafast electron and hole transfer between two photosensitizers (corrole and perylene diimide linked with oligopeptide and amino acids) where the through-bond distances between them should prohibit it. The report was published in the Proc. Natl. Acad. Sci. USA 2021, 118, e2026462118. doi: 10.1073/pnas.2026462118. Employing a combination of NMR, circular dichroism and computational studies, the researchers demonstrated that intramolecular hydrogen bonding brings both chromophores into proximity in a ‘scorpion-shaped’ molecular architecture, thereby enabling fast charge transfer. In other words, the revolutionary design implemented in this study encompasses intramolecular hydrogen bonds between the corrole core and an amide, as well as between the same amide and the pyerlene diimide, not only result in well-defined structural folds that are unusual for short pipettes, but also provide pathways for picosecond electron and hole transfer. This work provides guidelines for construction of effective donor-acceptor assemblies linked by long flexible bridges as well as insights into structural motifs for mediating charge transfer in proteins.

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