TY - JOUR
T1 - Size-Exclusion Mechanism Driving Host-Guest Interactions between Octahedral Rhenium Clusters and Cyclodextrins
AU - Ivanov, Anton A.
AU - Falaise, Clément
AU - Laouer, Kevin
AU - Hache, François
AU - Changenet, Pascale
AU - Mironov, Yuri V.
AU - Landy, David
AU - Molard, Yann
AU - Cordier, Stéphane
AU - Shestopalov, Michael A.
AU - Haouas, Mohamed
AU - Cadot, Emmanuel
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/10/7
Y1 - 2019/10/7
N2 - 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 [Re6Q8(CN)6]4- with Q = S, Se, and Te were performed, leading to six new crystal structures revealing different types of supramolecular arrangements. Encapsulation of [Re6Q8(CN)6]4- (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 [Re6S8(CN)6]4- 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.
AB - 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 [Re6Q8(CN)6]4- with Q = S, Se, and Te were performed, leading to six new crystal structures revealing different types of supramolecular arrangements. Encapsulation of [Re6Q8(CN)6]4- (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 [Re6S8(CN)6]4- 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.
U2 - 10.1021/acs.inorgchem.9b02048
DO - 10.1021/acs.inorgchem.9b02048
M3 - Article
C2 - 31553588
AN - SCOPUS:85072920997
SN - 0020-1669
VL - 58
SP - 13184
EP - 13194
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 19
ER -