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Host–Guest Binding Hierarchy within Redox‐ and Luminescence‐Responsive Supramolecular Self‐Assembly Based on Chalcogenide Clusters and γ‐Cyclodextrin
Author(s) -
Ivanov Anton A.,
Falaise Clément,
Abramov Pavel A.,
Shestopalov Michael A.,
Kirakci Kaplan,
Lang Kamil,
Moussawi Mhamad A.,
Sokolov Maxim N.,
Naumov Nikolay G.,
Floquet Sébastien,
Landy David,
Haouas Mohamed,
Brylev Konstantin A.,
Mironov Yuri V.,
Molard Yann,
Cordier Stéphane,
Cadot Emmanuel
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201802102
Subject(s) - supramolecular chemistry , crystallography , chemistry , chalcogenide , isothermal titration calorimetry , octahedron , luminescence , aqueous solution , crystal structure , stereochemistry , materials science , organic chemistry , optoelectronics
Abstract Water‐soluble salts of anionic [Re 6 Q 8 (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 [Re 6 S 8 (CN) 6 ] 4− interacts preferentially with the primary faces of the γ‐CD while the bulkier clusters [Re 6 Se 8 (CN) 6 ] 4− and [Re 6 Te 8 (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 [Re 6 S 8 (CN) 6 ] 4− or to 1D “bamboo‐like” columns with [Re 6 Se 8 (CN) 6 ] 4− and [Re 6 Te 8 (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.