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

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.
Document type :
Journal articles
Complete list of metadatas

Cited literature [34 references]  Display  Hide  Download

https://hal-univ-rennes1.archives-ouvertes.fr/hal-01863768
Contributor : Laurent Jonchère <>
Submitted on : Wednesday, August 29, 2018 - 1:38:50 PM
Last modification on : Thursday, May 23, 2019 - 6:24:04 PM
Long-term archiving on : Friday, November 30, 2018 - 3:13:45 PM

File

Ivanov et al_Host-Guest Bindin...
Files produced by the author(s)

Identifiers

Citation

Anton A Ivanov, Clément 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, Wiley-VCH Verlag, In press, ⟨10.1002/chem.201802102⟩. ⟨hal-01863768⟩

Share

Metrics

Record views

216

Files downloads

101