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Plates-formes supramoléculaires à l'échelle nanométrique : architectures fonctionnelles comme une étape vers l'électronique organique

Abstract : Achieving a subtle control over the interplay between various distinct weak interactions between molecular building blocks through a supramolecular design makes it possible the production of self-assembled nanomaterials. This is the chemists “bottom-up” approach to nanoscience and nanotechnology. Such a strategy when applied on programmed tectons provides access towards the fabrication of 1D, 2D and 3D nanoarchitectures with properties at will. Although the use of weak forces to control self-assembly attracted already a great attention1, many are the challenges which are still open in the field. In the framework of this thesis we have focused our attention to three main aspects: Control over 2D self-assembly, especially addressed to achieving a subtle control over the positioning of functional units and their organization, either with respect the substrate, or with respect to neighboring molecules.Expanding the 2D self-assembly to the third dimension, i.e. growing programmed architectures, layer by layer, in a rigidly restrained fashion; Reactivity on the surface, which besides the industrial appeal in the development of new more efficient catalyst, may pave the road towards the synthesis of 2D-conjugated thus (semi)conducting polymers as synthetic graphene-like alternatives. Three complementary topics, constituting the backbone of this thesis work, have been addressed by combining different physico-chemical methods including Scanning Tunneling Microscopy (STM), Molecular modeling relaying on instrumental and software development, respectively. Scanning tunneling Microscopy is a powerful tool to monitor nanoscale phenomena whereas through Simulations one could attain a precise understanding and define design principles.The first objective of this thesis work was to achieve a control over the forces governing the bi-dimensional self-assembly of different building blocks at surfaces and interfaces. To this end, different systems were considered, ranging from commercially available synthons, to most rare custom made building blocks. STM was employed to explore the self-assembly of the first generation of dendrimers on graphite at the solid-liquid interface2, providing direct insight into the effect on the supramolecular interactions. Particular attention was also paid to the study of the competition between different adsorbates – an aromatic polyol and a bypiridyn-pirimidin-amine, and to the modification of packing patterns upon addition of different metal salts, in-situ, as in the case of a functionalized porphyrinic tecton . Building up on such a knowledge on 2D self-assembly, we have extended to order at the solid-liquid interface to the third dimension. This was accomplished by designing and investigating a hetero-aromatic tetracarboxylic acid building block which was found to form a self-templated bi-layered structure3. The unique design principle relies on the presence of four carbonyl moieties inside the conjugated core which we were found playing different roles: (i) they represent ‘‘primary’’ recognition sites on the molecular building blocks, to promote the self-assembly into 2D porous layers, (ii) they offer a fine control of their conformational planarity, which confers the self- templating capacity, and (iii) they introduce secondary recognition sites, which mediate the interactions between the self- assembled layers. The capacity of forming 2D supramolecular architectures is a prerequisite towards their use for exploring surface reactions, thereby forming frameworks, where the weak forces responsible for the self-assembly are substituted with covalent bonds or strong metallo-ligand links, aiming to obtain infinite two dimensional conjugate network, which will likely cover a key role in the next generation of electronic materials.[...]
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Andrea Cadeddu. Plates-formes supramoléculaires à l'échelle nanométrique : architectures fonctionnelles comme une étape vers l'électronique organique. Other. Université de Strasbourg, 2012. English. ⟨NNT : 2012STRAF071⟩. ⟨tel-00954730⟩

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