Controlling the Host–Guest Interaction Mode through a Redox Stimulus. Issue 51 (23rd November 2017)

• Record Type: Journal Article
• Authors: Szalóki, György; Croué, Vincent; Carré, Vincent; Aubriet, Frédéric; Alévêque, Olivier; Levillain, Eric; Allain, Magali; Aragó, Juan; Ortí, Enrique; Goeb, Sébastien; Sallé, Marc
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 51(2017)
• Page Start: 16272
• Page End: 16276
• Publication Date: 2017-11-23
• Subjects: cage compounds -- host–guest systems -- self-assembly -- supramolecular chemistry -- tetrathiafulvalene; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201709483
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A proof‐of‐concept related to the redox‐control of the binding/releasing process in a host–guest system is achieved by designing a neutral and robust Pt‐based redox‐active metallacage involving two extended‐tetrathiafulvalene (exTTF) ligands. When neutral, the cage is able to bind a planar polyaromatic guest (coronene). Remarkably, the chemical or electrochemical oxidation of the host–guest complex leads to the reversible expulsion of the guest outside the cavity, which is assigned to a drastic change of the host–guest interaction mode, illustrating the key role of counteranions along the exchange process. The reversible process is supported by various experimental data ( 1 H NMR spectroscopy, ESI‐FTICR, and spectroelectrochemistry) as well as by in‐depth theoretical calculations performed at the density functional theory (DFT) level. Abstract : Stimuli‐responsive metallacages : A self‐assembled, redox‐active platinum cage constructed from an extended‐tetrathiafulvalene ligand can be reversibly oxidized to its stable tetracationic state. The reversible control of the cavity charge from 0 to 4+ makes it possible to tune the binding and releasing of a polyaromatic.