Photoredox-Switchable Resorcin[4]arene Cavitands: Radical Control of Molecular Gripping Machinery via Hydrogen Bonding

Abstract

Semiquinones (SQ) are generated in photosynthetic organisms upon photoinduced electron transfer to quinones (Q). 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 SQ 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 Q state until strengthening of HB upon reduction to the paramagnetic SQ radical anion provided stabilization of the closed form. The SQ 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.