Fully conjugated porphyrin nanorings combine an end-free π-system with well defined size and shape. They provide models for testing our understanding of light harvesting in natural photosynthetic systems, and may lead to the creation of new functional materials. This thesis describes the template-directed synthesis of novel 10, 16, 18, 20, 24, 30, 40 and 50-porphyrin nanorings using small templates, as well as the investigation of their structure, electronic properties and supramolecular chemistry in solution and on surfaces. This work illustrates the scope of Vernier templating as a tool for the synthesis of monodisperse molecules of unprecedented sizes. Chapter 1 introduces key properties of porphyrins and π-conjugated linear and cyclic porphyrin oligomers and describes the principle methods of preparing non-conjugated and conjugated cyclic polymers. It also covers recent advances in the synthesis of fully-conjugated porphyrin nanorings, in particular Vernier templating. Chapter 2 discusses the formation of higher order porphyrin nanorings (18- and 24-porphyrin nanorings) in the classical synthesis of 6-porphyrin nanoring and the Vernier-templated synthesis of 12-porphyrin nanoring. Chapter 3 describes the Vernier-templated synthesis of 24-porphyrin nanoring and its characterization. Chapter 4 shows that the flexibility of 24-porphyrin nanoring can be locked by the formation of a “sandwich” complex in the presence of a bidentate ligand or by solvent-induced formation of aggregates. Chapter 5 demonstrates the use of templates to control the cyclooligomerization of linear porphyrin oligomers. Vernier-templated synthetic routes to 10-, 30- and 40-porphyrin nanorings are investigated. Chapter 6 reports the electronic properties of porphyrin nanorings as probed by electrochemistry (for 6 porphyrin nanoring) or fluorescence anisotropy measurements (for 24 porphyrin nanoring). Crystal structures of 6 and 12 porphyrin nanoring template complexes are presented. Chapter 7 contains experimental procedures and characterization data of known and novel compounds synthesized in the course of this thesis.

Les travaux décrits dans ce manuscrit utilisent les principes de la tectonique moléculaire pour générer des polymères de coordination hautement fluorés et /ou chiraux pour une application potentielle en séparation chirale. La synthèse de 13 porphyrines de type A2B2 substituées en position méso par deux pyridines et par deux chaines fluorées et/ou alkyles a été mise au point. Des réseaux de coordination ont été obtenus en présence de Zn(II) et de Cd(II) et caractérisés par diffraction des RX sur monocristal (DRX). Une analyse systématique des interactions supramoléculaires et notamment de interactions F---F présentes à l’état solide a été conduite. Des réseaux à base de liaisons halogènes ont également été obtenus en présence de di- et tri-iodoarènes et caractérisés par DRX.Le premier chapitre est une introduction générale sur la tectonique moléculaire, le deuxième chapitre décrit les voies des synthèses utilisées pour générer les ligands chiraux et fluorés et leur caractérisation à l’état solide. Le troisième chapitre présente la structure des réseaux mono, bi, et tridimensionnels formés en présence de Zn(II) ou de Cd(II), l’analyse structurale met en évidence un nombre croissant d’interaction F---F en fonction du nombre de fluors présents à la périphérie du macrocycle porphyrinique. Le dernier chapitre se concentre sur l’utilisation des liaisons halogènes de type N---I impliquant des porphyrines ou des tectons de type bipyridine et une série d’ iodofluoroarenes. / This manuscript focuses on the use of molecular tectonics to generate chiral and / or fluorinated coordination polymers based on porphyrin building blocks for potential application in chiral separation. Synthesis of novel A2B2 fluorinated porphyrin tectons is described and their combinations with metal ions and haloarenes molecules are characterized by X-Ray diffraction.The first chapter gives a general introduction on molecular tectonics; the second chapter focuses on the synthetic routes used for the synthesis of highly fluorinated and/or chiral porphyrins and their solid state characterization by X-Ray diffraction analysis, highlighting the importance of the number of fluorine atoms present at the periphery of the tecton on the crystal packing. The third chapter presents the mono-, bi- and three dimensional networks formed by a combination of the porphyrins with Zn(II) or Cd(II). In the solid state, short F---F contacts were observed depending on the number of fluorine atoms present on the porphyrin backbone. The last chapter focuses on the use of halogen bonds, by merging the neutral porphyrin or bipyridine tectons with a series of iodofluoroarenes. The crystalline materials described in this work can be used as potential candidates for the separation of chiral and fluorinated molecules.