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Controlling handedness of triarylamine trisamide assemblies by means of circularly polarized light or chiral additives

Abstract : To pave the way for the absolute asymmetric catalysis, triarylamine trisamide (TATA) supramolecular helical polymers were investigated under the influence of circularly polarized light (CPL) and chiral additives/solvents. The association properties of TATA molecules with saturated or diacetylenic side chains were probed in presence and absence of CPL, by SANS, UV–Vis–NIR, FT–IR, NMR and EPR. The two types of self-assembly formed by these TATA molecules, non-specific aggregates and hydrogen-bonded helical stacks, are in competition and the majority assembly depends on conditions (concentration, temperature, solution/gel/solid). Light and the resulting radical cationic species do not strongly affect the structure of these assemblies, while the co-assembly between neutral and radical cationic species is demonstrated. In these co-assemblies, the unpaired electrons are either slowly delocalized in solution, because of the disorder in assemblies, or rapidly delocalized within long aligned fibers of thin films. Our CD study discards the possibility of using CPL to direct the handedness of TATA-SDA assemblies in the conditions stated in the literature. Finally, the synthesis of TATA ligands bearing a triphenylphosphine unit was achieved. Their study in toluene, dichloromethane and decalin showed the thermoreversible formation of long hydrogen-bonded stacks. Despite the use of a library of enantiopure small molecules as chiral additives or solvents, no biased supramolecular helices were detected. The in-depth characterization of assemblies carried out in this thesis paves the way towards a better control of the structure of functionalized helical assemblies.
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Submitted on : Wednesday, July 13, 2022 - 2:03:11 PM
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  • HAL Id : tel-03722467, version 1

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Quentin Sallembien. Controlling handedness of triarylamine trisamide assemblies by means of circularly polarized light or chiral additives. Organic chemistry. Sorbonne Université, 2021. English. ⟨NNT : 2021SORUS499⟩. ⟨tel-03722467⟩

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