Size-Exclusion Mechanism Driving Host-Guest Interactions between Octahedral Rhenium Clusters and Cyclodextrins

Anton A Ivanov (1, 2) , Clement Falaise (1) , Kevin Laouer (3) , François Hache (3) , Pascale Changenet (3) , Yuri V Mironov (4, 2) , David Landy (5) , Yann Molard (6) , Stéphane Cordier (6) , Michael A Shestopalov (4, 2) , Mohamed Haouas (1) , Emmanuel Cadot (1)

1 ILV - Institut Lavoisier de Versailles
2 NIC - Nikolaev Institute of Inorganic Chemistry [Novosibirsk]
3 LOB - Laboratoire d'Optique et Biosciences
4 NSU - Novosibirsk State University
5 UCEIV - Unité de Chimie Environnementale et Interactions sur le Vivant
6 ISCR - Institut des Sciences Chimiques de Rennes

In aqueous solution, cyclodextrins (CDs) are able to bind strongly either hydrophobic species or also hydrophilic molecules such as octahedral hexametallic cluster. Systematic investigation of the reactivity between native CDs (α- or β-CD) and water-soluble rhenium clusters [ReQ(CN)] with Q = S, Se, and Te were performed, leading to six new crystal structures revealing different types of supramolecular arrangements. Encapsulation of [ReQ(CN)] (Q = S, Se, or Te) within two β-CDs is observed regardless of the cluster size. Interestingly, different assembling scenarios are pointed out depending on the host-guest matching featured by no, partial, or deep inclusion complexes that involved either primary or secondary rim of the CD tori. In the specific case of α-CD, only the smaller cluster [ReS(CN)] is able to form inclusion complex with the tori host. Solution investigations, using a set of complementary techniques including isothermal titration calorimetry, multinuclear NMR methods, cyclic voltammetry, and electrospray ionization mass spectrometry, corroborate nicely conclusions of the solid-state studies. It appears clearly that size-matching supported by solvent effects play key roles in the stability of the host-guest complexes. At last, circular dichroism studies underline that the chirality induction from cyclodextrins to the rhenium cluster depends strongly on the strength of host-guest interactions.

Domaines: Chimie

Anton A Ivanov, Clement Falaise, Kevin Laouer, François Hache, Pascale Changenet, et al.. Size-Exclusion Mechanism Driving Host-Guest Interactions between Octahedral Rhenium Clusters and Cyclodextrins. Inorganic Chemistry, 2019, 58 (19), pp.13184-13194. ⟨10.1021/acs.inorgchem.9b02048⟩. ⟨hal-02307027⟩