Size-Exclusion Mechanism Driving Host-Guest Interactions between Octahedral Rhenium Clusters and Cyclodextrins - Archive ouverte HAL Access content directly
Journal Articles Inorganic Chemistry Year : 2019

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

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François Hache
Pascale Changenet
Mohamed Haouas
Emmanuel Cadot

Abstract

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.
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Dates and versions

hal-02307027 , version 1 (10-01-2021)

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Cite

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⟩
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