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

Water-soluble salts of anionic [Re6 Q8 (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 [Re6 S8 (CN)6 ]4- interacts preferentially with the primary faces of the γ-CD while the bulkier clusters [Re6 Se8 (CN)6 ]4- and [Re6 Te8 (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 [Re6 S8 (CN)6 ]4- or to 1D "bamboo-like" columns with [Re6 Se8 (CN)6 ]4- and [Re6 Te8 (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.