| Autor: |
Moussawi MA; Institut Lavoisier de Versailles, UMR 8180, UVSQ, Université Paris-Saclay , 78035 Versailles, France., Leclerc-Laronze N; Institut Lavoisier de Versailles, UMR 8180, UVSQ, Université Paris-Saclay , 78035 Versailles, France., Floquet S; Institut Lavoisier de Versailles, UMR 8180, UVSQ, Université Paris-Saclay , 78035 Versailles, France., Abramov PA; Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences , Novosibirsk 630090, Russia.; Novosibirsk State University , Novosibirsk 630090, Russia., Sokolov MN; Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences , Novosibirsk 630090, Russia.; Novosibirsk State University , Novosibirsk 630090, Russia., Cordier S; Institut des Sciences Chimiques de Rennes, UMR 6226, Université de Rennes 1 , 35042 Rennes, France., Ponchel A; Unité de Catalyse et Chimie du Solide, UMR 8181, Univ. Artois, CNRS, Centrale Lille, ENSCL, Univ. Lille 1 , 62300 Lens, France., Monflier E; Unité de Catalyse et Chimie du Solide, UMR 8181, Univ. Artois, CNRS, Centrale Lille, ENSCL, Univ. Lille 1 , 62300 Lens, France., Bricout H; Unité de Catalyse et Chimie du Solide, UMR 8181, Univ. Artois, CNRS, Centrale Lille, ENSCL, Univ. Lille 1 , 62300 Lens, France., Landy D; Unité de Chimie Environnementale et Interactions sur le Vivant EA 4492, SFR Condorcet FR CNRS 3417, Université du Littoral Côte d'Opale , 59140 Dunkerque, France., Haouas M; Institut Lavoisier de Versailles, UMR 8180, UVSQ, Université Paris-Saclay , 78035 Versailles, France., Marrot J; Institut Lavoisier de Versailles, UMR 8180, UVSQ, Université Paris-Saclay , 78035 Versailles, France., Cadot E; Institut Lavoisier de Versailles, UMR 8180, UVSQ, Université Paris-Saclay , 78035 Versailles, France. |
| Abstrakt: |
Herein, we report on a three-component supramolecular hybrid system built from specific recognition processes involving a Dawson-type polyoxometalate (POM), [P 2 W 18 O 62 ] 6- , a cationic electron-rich cluster [Ta 6 Br 12 (H 2 O) 6 ] 2+ , and γ-cyclodextrin (γ-CD). Such materials have been investigated using a bottom-up approach by studying the specific interactions between γ-CD and both types of inorganic units. Their ability to interact has been investigated in the solid state by single-crystal X-ray diffraction (XRD) and in solution using multinuclear NMR methods (including DOSY, EXSY, and COSY), electrospray ionization mass and UV-vis spectroscopies, electrochemistry, and isothermal titration calorimetry experiments. Single-crystal XRD analysis reveals that POM:γ-CD constitutes a highly versatile system which gives aggregates with 1:1, 1:2, and 1:3 stoichiometry. Surprisingly, these arrangements exhibit a common feature wherein the γ-CD moiety interacts with the Dawson-type POMs through its primary face. We present also the first structural model involving an octahedral-type metallic cluster with γ-CD. XRD study reveals that the cationic [Ta 6 Br 12 (H 2 O) 6 ] 2+ ion is closely embedded within two γ-CD units to give a supramolecular ditopic cation, suitable to be used as a linker within extended structure. Solution study demonstrates clearly that pre-associations exist in solution, for which binding constants and thermodynamic parameters have been determined, giving preliminary arguments about the chaotropic nature of the inorganic ions. Finally, both building blocks, i.e., the ditopic supramolecular cation {[Ta 6 Br 12 (H 2 O) 6 ]@2CD} 2+ and the Dawson-type anion, react together to give a three-component, well-ordered hybrid material derived either as a supramolecular hydrogel or single crystals. The solid-state structure shows an unprecedented helicoidal tubular chain resulting from the periodic alternation of POM and supramolecular cation, featuring short hydrogen-bonding contacts between the electron-poor POM and electron-rich cluster. The 1D tubular ionic polymer observed in the single crystals should make it possible to understand the long-range ordering observed within the hydrogel hybrid material. The supramolecular chemical complementarities between the γ-CD-based ditopic cation and POM open a wide scope for the design of hybrid materials that accumulate synergistic functionalities. |
