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Theses

Activation par transfert d'électron : applications aux systèmes commutables et à l'ingénierie moléculaire

Abstract : One of the most important key to the development of nanosciences lies in our ability to monitor, modify or control nanometric materials. The addition or removal of electrons to or from given molecular objects can find useful applications in numerous arena of nanosciences: as signal transcription of interactions processes, as impulse to trigger conformational, configurational or directional mechanical changes at the molecular level or even as a way to control and activate the reactivity of molecular building blocks in organic synthesis. This work deals with two complementary processes associated to electron transfer: molecular movements in switchable architectures and activation of molecular building blocks to form conjugated macrocyclic structures The first part of this research work is devoted to the synthesis of porphyrin-based molecular tweezers and of ferrocene-based molecular pivots. The dynamic properties of these switchable molecular objects; relying on reversible π-dimerization processes, have been investigated by spectroscopic, electrochemical and spectroelectrochemical methods. In the second part of this manuscript we show few examples of electrochemically driven synthetic procedures for preparation of expanded porphyrins. Unlike chemical oxidants, which must often be tested empirically for a given transformation, under electrochemical conditions, one has the opportunity to tune the reactivity of the pyrrole-based reagent via the choice of anodic voltage. We especially established that the use of bipyrrole allows for the clean and high-yield production of cyclo[8]pyrrole; the requisite electrochemically-induced cyclization of four bipyrrole building blocks likely involving an electrolyte-based templating effect. The success of this approach leads us to propose that analogous electrochemical oxidation processes could be used to generate a range of new expanded porphyrin products.
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https://tel.archives-ouvertes.fr/tel-00553066
Contributor : Adriana Iordache <>
Submitted on : Thursday, January 6, 2011 - 2:27:19 PM
Last modification on : Friday, November 6, 2020 - 3:48:33 AM
Long-term archiving on: : Saturday, December 3, 2016 - 2:35:38 AM

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  • HAL Id : tel-00553066, version 1

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Citation

Adriana Iordache. Activation par transfert d'électron : applications aux systèmes commutables et à l'ingénierie moléculaire. Chimie. Université Joseph-Fourier - Grenoble I, 2010. Français. ⟨tel-00553066⟩

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