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Conception, synthèse et caractérisations de MOFs à base de porphyrines

Abstract : Porphyrins are important macrocyclic compounds which are prevalent in nature and have been extensively studied by chemists in homogeneous catalysis as enzyme mimics. Incorporating porphyrins in metal-organic frameworks (MOFs) offer an ideal opportunity to obtain material with extended frameworks possessing the same properties as the homogenous systems. Much work has been done on porphyrinic MOFs but their stability remains a problem and a major limitation for possible wide scale applications. In literature, more stable MOFs have been realised using high valent metal ions in the inorganic building unit (such as Fe3+, Al3+, Zr4+) and/or by using more basic functionalities in the organic linker. However, regarding porphyrinic MOFs, little work is reported with ligands based on functionalities other than carboxylic acid groups. Therefore, our work focused on investigating the reactivity of porphyrinic ligands carrying various functionalities with high valent metal ions. More precisely, we focused on the design, synthesis optimisation and characterisation of such materials. This included studying existing stable carboxylate porphyrinic frameworks with a goal of incorporating new functionalities, which led to new variations of these materials. Our work also demonstrated that the framework topologies observed with carboxylate based porphyrinic ligand can be expanded to other functionalities with the synthesis of a new tetrazolate based porphyrinic MOF. MOF synthesis was also investigated with phenolate functionalised ligands and resulted in the first gallate based porphyrinic MOF reported. The stability of this new material was assessed. This manuscript discusses the synthesis and the characterisation of these MOFs via a combination of experimental techniques (X-ray diffraction, TGA analysis, UV-vis spectroscopy, IR-spectroscopy, sorption studies etc.). The preliminary evaluation of the catalytic activity of some of the MOFs is also described
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Submitted on : Monday, March 12, 2018 - 3:21:10 PM
Last modification on : Thursday, June 4, 2020 - 3:08:02 PM
Long-term archiving on: : Wednesday, June 13, 2018 - 2:24:11 PM


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  • HAL Id : tel-01729322, version 1



Brian Abeykoon. Conception, synthèse et caractérisations de MOFs à base de porphyrines. Autre. Université de Lyon, 2017. Français. ⟨NNT : 2017LYSE1259⟩. ⟨tel-01729322⟩



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