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Asterisk-Shaped Arenes and Heteroarenes Incorporating Sulfur, Oxygen and Nitrogen: Synthesis, Structures, Photophysics, Dynamic and Supramolecular Covalent Chemistry.

Abstract : The content of this thesis focusses on functionalized and branched polysulfurated, polyoxygenated or polycyanated molecular asterisks incorporating either a benzene, a pyridine or a pyrene core. The main objectives are to report the synthesis and the structural, photophysical, supramolecular and covalent dynamic properties of the newly created molecular architectures, in order to develop further uses and applications of them in a near future, toward molecular electronics, imaging, materials and life sciences in general. This work also tackles the relation between topology and optoelectronic properties for opening a new direction and future perspectives in materials science and polyaromatic chemistry. It also questions some fundamental principles and mechanisms in organic chemistry, notably the reversibility of a main and historical mechanism in organic chemistry: the nucleophilic aromatic substitution, which is known since 1854. At first, the thesis covers new synthetic approaches to functionalize pyrene in its K-region, which has been neglected in spite of the historical importance of pyrenes in optoelectronic sensing, materials and biological sciences. It is followed by the synthesis of various sulfurated, oxygenated and cyanated molecular asterisks with a benzene or pyridine core, in search for a new field in dynamic covalent chemistry (DCC) with arenes and heteroarenes, by implementing and promoting reversible nucleophilic aromatic substitutions in DCC, while at the same time developing all-organic highly phosphorescent smart materials via a rigidity-induced phosphorescence (RIP) phenomena. Thus, we report the "Sulfur Dance" around arenes and heteroarenes from a reversible exchange of sulfur components around an aromatic template, a new process in aromatic chemistry. In order to study reversible SNAr reactions, several reaction conditions, substituent effects, analytical and separative methods were necessary in DCC for anayzing the created library of compounds. In that direction, we also analyzed the importance of π-extended sulfurated and oxygenated asterisks with a benzene core, incorporting phenyl, biphenyl, naphthyl or heteroaromatic arms, in search for some exalted photohysical properties or metal cations bindings of uses in supramolecular chemistry. Thereofore, this thesis covers broad areas of aromatic chemistry, basic reaction mechanisms, photophysics and dynamic covalent and supramolecular chemistry, towards materials and life sciences.
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Submitted on : Friday, February 25, 2022 - 5:18:08 PM
Last modification on : Wednesday, March 2, 2022 - 3:35:08 AM


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Sapna Gahlot. Asterisk-Shaped Arenes and Heteroarenes Incorporating Sulfur, Oxygen and Nitrogen: Synthesis, Structures, Photophysics, Dynamic and Supramolecular Covalent Chemistry.. Organic chemistry. Aix-Marseille Université, 2022. English. ⟨tel-03589656⟩



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