Controlling the Host-Guest Interaction Mode Through a Redox Stimulus

Angew Chem Int Ed Engl. 2017 Dec 18;56(51):16272-16276. doi: 10.1002/anie.201709483. Epub 2017 Nov 23.

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.

Keywords: cage compounds; host-guest systems; self-assembly; supramolecular chemistry; tetrathiafulvalene.

Publication types

  • Research Support, Non-U.S. Gov't