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- Title
Photoredox‐Switchable Resorcin[4]arene Cavitands: Radical Control of Molecular Gripping Machinery via Hydrogen Bonding.
- Authors
Milić, Jovana; Zalibera, Michal; Talaat, Darius; Nomrowski, Julia; Trapp, Nils; Ruhlmann, Laurent; Boudon, Corinne; Wenger, Oliver S.; Savitsky, Anton; Lubitz, Wolfgang; Diederich, François
- Abstract
Abstract: Semiquinones (<bold>SQ</bold>) are generated in photosynthetic organisms upon photoinduced electron transfer to quinones (<bold>Q</bold>). They are stabilized by hydrogen bonding (HB) with the neighboring residues, which alters the properties of the reaction center. We designed, synthesized, and investigated resorcin[4]arene cavitands inspired by this function of <bold>SQ</bold> in natural photosynthesis. Cavitands were equipped with alternating quinone and quinoxaline walls bearing hydrogen bond donor groups (HBD). Different HBD were analyzed that mimic natural amino acids, such as imidazole and indole, along with their analogues, pyrrole and pyrazole. Pyrroles were identified as the most promising candidates that enabled the cavitands to remain open in the <bold>Q</bold> state until strengthening of HB upon reduction to the paramagnetic <bold>SQ</bold> radical anion provided stabilization of the closed form. The <bold>SQ</bold> state was generated electrochemically and photochemically, whereas properties were studied by UV/Vis spectroelectrochemistry, transient absorption, and EPR spectroscopy. This study demonstrates a photoredox‐controlled conformational switch towards a new generation of molecular grippers.
- Subjects
RESORCINARENES; HYDROGEN bonding; SEMIQUINONE; CAVITANDS; PHOTOSYNTHESIS kinetics; QUINOXALINE compounds
- Publication
Chemistry - A European Journal, 2018, Vol 24, Issue 6, p1431
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201704788