Host-Guest Binding Hierarchy within Redox- and Luminescence-Responsive Supramolecular Self-Assembly Based on Chalcogenide Clusters and γ-Cyclodextrin

Anton A. Ivanov, Clément Falaise, Pavel A. Abramov, Michael A. Shestopalov, Kaplan Kirakci, Kamil Lang, Mhamad A. Moussawi, Maxim N. Sokolov, Nikolay G. Naumov, Sébastien Floquet, David Landy, Mohamed Haouas, Konstantin A. Brylev, Yuri V. Mironov, Yann Molard, Stéphane Cordier, Emmanuel Cadot

Результат исследования: Научные публикации в периодических изданияхстатья

19 Цитирования (Scopus)

Аннотация

Water-soluble salts of anionic [Re6Q8(CN)6]4- (Q=S, Se, Te) chalcogenide octahedral rhenium clusters react with γ-cyclodextrin (γ-CD) producing a new type of inclusion compounds. Crystal structures determined through single-crystal X-ray diffraction analysis revealed supramolecular host-guest assemblies resulting from close encapsulations of the octahedral cluster within two γ-CDs. Interestingly, nature of the inner Q ligands influences strongly the host-guest conformation. The cluster [Re6S8(CN)6]4- interacts preferentially with the primary faces of the γ-CD while the bulkier clusters [Re6Se8(CN)6]4- and [Re6Te8(CN)6]4- exhibit specific interactions with the secondary faces of the cyclic host. Furthermore, analysis of the crystal packing reveals additional supramolecular interactions that lead to 2D infinite arrangements with [Re6S8(CN)6]4- or to 1D "bamboo-like" columns with [Re6Se8(CN)6]4- and [Re6Te8(CN)6]4- species. Solution studies, using multinuclear NMR methods, ESI-MS and Isothermal titration calorimetry (ITC) corroborates nicely the solid-state investigations showing that supramolecular pre-organization is retained in aqueous solution even in diluted conditions. Furthermore, ITC analysis showed that host-guest stability increases significantly ongoing from S to Te. At last, we report herein that deep inclusion alters significantly the intrinsic physical-chemical properties of the octahedral clusters, allowing redox tuning and near IR luminescence enhancement.

Язык оригиналаанглийский
Страницы (с-по)13467-13478
Число страниц12
ЖурналChemistry - A European Journal
Том24
Номер выпуска51
DOI
СостояниеОпубликовано - 12 сен 2018

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