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

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.

KW - CHALCOGENIDE CLUSTERS

KW - MOLECULAR RECOGNITION

KW - GAMMA-CYCLODEXTRIN

KW - COMPLEXATION

KW - BINDING

KW - POLYOXOMETALATE

KW - ANION

KW - CUCURBITURIL

KW - LUMINESCENCE

UR - http://www.scopus.com/inward/record.url?scp=85072920997&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.9b02048

DO - 10.1021/acs.inorgchem.9b02048

M3 - Article

C2 - 31553588

AN - SCOPUS:85072920997

VL - 58

SP - 13184

EP - 13194

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 19

ER -