Metalla‐Assembled Electron‐Rich Tweezers: Redox‐Controlled Guest Release Through Supramolecular Dimerization. Issue 2 (20th November 2019)

• Record Type: Journal Article
• Authors: Krykun, Serhii; Dekhtiarenko, Maksym; Canevet, David; Carré, Vincent; Aubriet, Frédéric; Levillain, Eric; Allain, Magali; Voitenko, Zoia; Sallé, Marc; Goeb, Sébastien
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 2(2020)
• Page Start: 716
• Page End: 720
• Publication Date: 2019-11-20
• Subjects: host-guest systems -- molecular tweezers -- self-assembly -- sulfur heterocycles -- supramolecular chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201912016
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Developing methodologies for on‐demand control of the release of a molecular guest requires the rational design of stimuli‐responsive hosts with functional cavities. While a substantial number of responsive metallacages have already been described, the case of coordination‐tweezers has been less explored. Herein, we report the first example of a redox‐triggered guest release from a metalla‐assembled tweezer. This tweezer incorporates two redox‐active panels constructed from the electron‐rich 9‐(1, 3‐dithiol‐2‐ylidene)fluorene unit that are facing each other. It dimerizes spontaneously in solution and the resulting interpenetrated supramolecular structure can dissociate in the presence of an electron‐poor planar unit, forming a 1:1 host–guest complex. This complex dissociates upon tweezer oxidation/dimerization, offering an original redox‐triggered molecular delivery pathway. Abstract : A pair of molecular tweezers : A redox‐active coordination tweezer constructed from the dithiol‐fluorene framework spontaneously dimerizes in solution due to favorable geometric and electronic parameters. The interpenetrated dimer can dissociate upon forming a 1:1 host–guest complex in the presence of an electron‐poor guest, which can be reversibly released upon oxidation through an exchange process.