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Assemblages à base de polyoxométallates : des interactions fondamentales aux matériaux hybrides supramoléculaires

Abstract : In this work, we report in the first part the substitution of molybdenum by tungsten within Keplerate-type anions [{Mo6}12Mo30O312E60(AcO)30]42- (E = O or S). Introducing tungsten to the synthesis medium resulted in the isolation of a series of compounds, [{WxMo6- x}12Mo30O312E60(AcO)30]42, with variable metal content within their pentagonal units {M6}. An outstanding observation revealed the selective occupation of the central position in the pentagonal unit by the W atoms. This revelation was stretched to reach other historical structures as Mo-blue wheel [Mo154O462H14(H2O)70]14- and Krebs [Mo36O112(H2O)16]8- anions that also showed the same preferential occupation of W atoms for the heptacoordinated site. In the second part, we focus on the fabrication of a three-component hybrid material based on polyoxometalates (POMs), metallic clusters and -cyclodextrin ( -CD). Investigation of such material has been conducted using bottom-up approach by investigating the specific interactions between CD and both types ofinorganic units. Finally, the three componentsassociate together to give a well orderedpolymer-like hybrid chain that is derived ashydrogel and single crystals. In the last part, we extend the CD-POMinvestigation to reach giant POM structures asthe Mo-blue ring. A non-conventional complexation results from this interaction explained by the encapsulation of the organic macrocycle within the inorganic torus. Increasing the complexity of the system by introducing a third species provoked the formation of a hierarchical hybrid assembly.
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Submitted on : Wednesday, February 28, 2018 - 10:27:08 AM
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  • HAL Id : tel-01719282, version 1



Mhamad Aly Moussawi. Assemblages à base de polyoxométallates : des interactions fondamentales aux matériaux hybrides supramoléculaires. Chimie organique. Université Paris-Saclay, 2017. Français. ⟨NNT : 2017SACLV078⟩. ⟨tel-01719282⟩



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