Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 56, Issue 51, Pages 16272-16276Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201709483
Keywords
cage compounds; host-guest systems; self-assembly; supramolecular chemistry; tetrathiafulvalene
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Funding
- ANR JCJC [ANR-14-CE08-0001 BOMBER]
- Spanish Ministry of Economy and Competitiveness MINECO [CTQ2015-71154-P]
- Spanish Ministry of Economy and Competitiveness MINECO (Unidad de Excelencia Maria de Maeztu) [MDM-2015-0538]
- Generalitat Valenciana [PROMETEO/2016/135]
- European FEDER funds [CTQ2015-71154-P]
- MINECO
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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 (H-1 NMR spectroscopy, ESI-FTICR, and spectroelectrochemistry) as well as by in-depth theoretical calculations performed at the density functional theory (DFT) level.
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