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Controlling the Host–Guest Interaction Mode through a Redox Stimulus
Author(s) -
Szalóki György,
Croué Vincent,
Carré Vincent,
Aubriet Frédéric,
Alévêque Olivier,
Levillain Eric,
Allain Magali,
Aragó Juan,
Ortí Enrique,
Goeb Sébastien,
Sallé Marc
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201709483
Subject(s) - chemistry , redox , tetrathiafulvalene , density functional theory , coronene , electrochemistry , photochemistry , nanotechnology , molecule , computational chemistry , inorganic chemistry , electrode , materials science , organic chemistry
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.