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

0492669 - ÚACH 2019 RIV DE eng J - Článek v odborném periodiku
Ivanov, A. A. - Falaise, C. - Abramov, P. A. - Shestopalov, M.A. - Kirakci, Kaplan - Lang, Kamil - Moussawi, M. A. - Sokolov, M. N. - Naumov, N. G. - Floquet, S. - Landy, D. - Haouas, M. - Brylev, K. A. - Mironov, Y.V. - Molard, Y. - Cordier, S. - Cadot, E.
Host-Guest Binding Hierarchy within Redox- and Luminescence-Responsive Supramolecular Self-Assembly Based on Chalcogenide Clusters and γ-Cyclodextrin.
Chemistry - A European Journal. Roč. 24, č. 51 (2018), s. 13467-13478. ISSN 0947-6539. E-ISSN 1521-3765
Grant CEP: GA ČR(CZ) GA18-05076S
Institucionální podpora: RVO:61388980
Klíčová slova: Cyclodextrin * Electrochemistry * Luminescence * Metal cluster complex * Supramolecular self-assembly
Obor OECD: Inorganic and nuclear chemistry
Impakt faktor: 5.160, rok: 2018

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.
Trvalý link: http://hdl.handle.net/11104/0287093