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.

Institut des Sciences Chimiques de Rennes UMR 6226 CNRS Université de Rennes 1 Avenue du Général Leclerc 35042 Rennes France

Institut Lavoisier de Versailles CNRS UVSQ Université Paris Saclay 45 avenue des Etats Unis 78035 Versailles France

Institute of Inorganic Chemistry of the Czech Academy of Sciences Husinec Řež 1001 250 68 Řež Czech Republic

Nikolaev Institute of Inorganic Chemistry SB RAS 3 acad Lavrentiev ave 630090 Novosibirsk Russia

Novosibirsk State University 2 Pirogova st 630090 Novosibirsk Russia

The Federal Research Center of Fundamental and Translational Medicine 2 Timakova st 630117 Novosibirsk Russia

Unité de Chimie Environnementale et Interactions sur le Vivant 145 Avenue Maurice Schumann MREI 1 59140 Dunkerque France

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Face-Fusion of Icosahedral Boron Hydride Increases Affinity to γ-Cyclodextrin: closo,closo-[B21 H18 ]- as an Anion with Very Low Free Energy of Dehydration