G. Szalóki, V. Croué, V. Carré, F. Aubriet, O. Alévêque, E. Levillain, M. Allain, J. Aragó, E. Ortí, S. Goeb, M. Sallé
Angew. Chem. Int. Ed. 56 16272-16276 (2017). DOI

Travail réalisé sur le site de l’Université de Lorraine.

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 (1H NMR spectroscopy, ESI-FTICR, and spectroelectrochemistry) as well as by in-depth theoretical calculations performed at the density functional theory (DFT) level.