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Synthèse, structure et dynamique de rotors moléculaires cristallins

Abstract : In the context of spectacular developments in the field of molecular machines, the purpose of this work is to construct crystalline amphidynamic solids incorporating functional 1,4-diethynylbicyclo[2.2.2]octane (BCO) that are either self-assembled or organized by coordination to a metal. These chiral rotors have two degrees of freedom characterized in the solid state by variable temperature 1H spin-lattice relaxation experiments (rotational degree of freedom) or second-harmonic generation experiments (torsional degree of freedom of the helix blades). By coupling solid-state NMR experiments on static polycrystalline samples (experimental rotational barriers and frequency of rotational motion) to intermolecular interaction energy calculations of a rotor with its environment (rotational barriers), we show how the analysis of hydrogen bonding interactions is essential to understand the dynamics of the systems. In parallel, the non-linear optical nonlinearities recorded for every single crystalline rotor is seen as evidence for a random dynamic conformational switching in the handedness of the rotor helices which can undergo mutations while preserving the average space inversion symmetry of the lattice. In order to exploit this property, strategies of organic synthesis and crystal engineering have been implemented to direct the self-assembly of the rotators thereby providing objects for which the presence of a nonlinear optical response may be correlated with the dimensionality of the system.
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https://tel.archives-ouvertes.fr/tel-01064323
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Submitted on : Tuesday, September 16, 2014 - 9:59:30 AM
Last modification on : Thursday, December 9, 2021 - 3:46:03 PM
Long-term archiving on: : Wednesday, December 17, 2014 - 10:30:58 AM

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  • HAL Id : tel-01064323, version 1

Citation

Guillaume Bastien. Synthèse, structure et dynamique de rotors moléculaires cristallins. Chimie organique. Université d'Angers, 2013. Français. ⟨tel-01064323⟩

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