Université d'Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou, 2 bd Lavoisier, 49045, Angers Cedex, France.
LCP-A2MC, FR 3624, Université de Lorraine, ICPM, 1 boulevard Arago, 57078, Metz Cedex 03, France.
Angew Chem Int Ed Engl. 2017 Dec 18;56(51):16272-16276. doi: 10.1002/anie.201709483. Epub 2017 Nov 23.
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 NMR spectroscopy, ESI-FTICR, and spectroelectrochemistry) as well as by in-depth theoretical calculations performed at the density functional theory (DFT) level.
通过设计一种包含两个扩展的四硫富瓦烯（exTTF）配体的中性且坚固的基于铂的氧化还原活性金属笼，实现了主体-客体系统中结合/释放过程的氧化还原控制的概念验证。在中性状态下，笼能够结合一个平面多环芳烃客体（蒄）。值得注意的是，主体-客体配合物的化学或电化学氧化导致客体可逆地被逐出腔外，这归因于主体-客体相互作用模式的剧烈变化，说明了抗衡阴离子在交换过程中的关键作用。这一可逆过程得到了各种实验数据（H NMR 光谱、ESI-FTICR 和光谱电化学）以及在密度泛函理论（DFT）水平上进行的深入理论计算的支持。
