TY - JOUR

T1 - Host-Guest Binding Hierarchy within Redox- and Luminescence-Responsive Supramolecular Self-Assembly Based on Chalcogenide Clusters and γ-Cyclodextrin

AU - Ivanov, Anton A.

AU - Falaise, Clément

AU - Abramov, Pavel A.

AU - Shestopalov, Michael A.

AU - Kirakci, Kaplan

AU - Lang, Kamil

AU - Moussawi, Mhamad A.

AU - Sokolov, Maxim N.

AU - Naumov, Nikolay G.

AU - Floquet, Sébastien

AU - Landy, David

AU - Haouas, Mohamed

AU - Brylev, Konstantin A.

AU - Mironov, Yuri V.

AU - Molard, Yann

AU - Cordier, Stéphane

AU - Cadot, Emmanuel

N1 - Publisher Copyright: © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2018/9/12

Y1 - 2018/9/12

N2 - Water-soluble salts of anionic [Re6Q8(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 [Re6S8(CN)6]4- interacts preferentially with the primary faces of the γ-CD while the bulkier clusters [Re6Se8(CN)6]4- and [Re6Te8(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 [Re6S8(CN)6]4- or to 1D "bamboo-like" columns with [Re6Se8(CN)6]4- and [Re6Te8(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.

AB - Water-soluble salts of anionic [Re6Q8(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 [Re6S8(CN)6]4- interacts preferentially with the primary faces of the γ-CD while the bulkier clusters [Re6Se8(CN)6]4- and [Re6Te8(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 [Re6S8(CN)6]4- or to 1D "bamboo-like" columns with [Re6Se8(CN)6]4- and [Re6Te8(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.

KW - Cyclodextrin

KW - Electrochemistry

KW - Luminescence

KW - Metal cluster complex

KW - Supramolecular self-assembly

KW - luminescence

KW - electrochemistry

KW - metal cluster complex

KW - supramolecular self-assembly

KW - cyclodextrin

KW - BUILDING-BLOCKS

KW - SINGLET OXYGEN PRODUCTION

KW - CELLULAR INTERNALIZATION

KW - CRYSTAL-STRUCTURES

KW - PHOTOPHYSICAL PROPERTIES

KW - IODIDE CLUSTER

KW - HYBRID MATERIALS

KW - METAL-ORGANIC FRAMEWORKS

KW - RAY CONTRAST AGENT

KW - BETA-CYCLODEXTRIN

UR - http://www.scopus.com/inward/record.url?scp=85051032384&partnerID=8YFLogxK

U2 - 10.1002/chem.201802102

DO - 10.1002/chem.201802102

M3 - Article

C2 - 29894019

AN - SCOPUS:85051032384

VL - 24

SP - 13467

EP - 13478

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 51

ER -