Host-Guest Binding Hierarchy within Redox- and Luminescence-Responsive Supramolecular Self-Assembly Based on Chalcogenide Clusters and γ-Cyclodextrin - Université de Rennes Access content directly
Journal Articles Chemistry - A European Journal Year : 2018

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

Clement Falaise
Pavel A Abramov
  • Function : Correspondent author
Sébastien Floquet
Yann Molard
Emmanuel Cadot

Abstract

Water-soluble salts of anionic [Re Q (CN) ] (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 [Re S (CN) ] interacts preferentially with the primary faces of the γ-CD while the bulkier clusters [Re Se (CN) ] and [Re Te (CN) ] 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 [Re S (CN) ] or to 1D "bamboo-like" columns with [Re Se (CN) ] and [Re Te (CN) ] 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.
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Dates and versions

hal-01863768 , version 1 (29-08-2018)

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Anton A Ivanov, Clement Falaise, Pavel A Abramov, Michael A Shestopalov, Kaplan Kirakci, et al.. Host-Guest Binding Hierarchy within Redox- and Luminescence-Responsive Supramolecular Self-Assembly Based on Chalcogenide Clusters and γ-Cyclodextrin. Chemistry - A European Journal, 2018, 24 (51), pp.13467-13478. ⟨10.1002/chem.201802102⟩. ⟨hal-01863768⟩
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