Cocrystals have attracted much interest in recent years. It was once thought that cocrystals could be a means to prevent polymorphism but many recent examples of cocrystal polymorphism have been discovered and reported. In this contribution, we present a survey of polymorphic cocrystals. Polymorphism is the ability of a specific chemical compound to crystallize in more than one crystalline form. Polymorphs have different arrangements of the molecules in the given crystal lattice and may exhibit different characteristics such as packing properties, thermodynamic properties, spectroscopic properties, kinetic properties, surface properties, and mechanical properties. Polymorphs can be classified in various groups such as crystalline, amorphous, hydrates, and solvates. The main characterization methods used in this thesis are X-ray diffraction and solid-state NMR spectroscopy. The concept of variable stoichiometry cocrystallization is explored in halogen-bonded systems. Three novel cocrystals of 1,4-diiodotetrafluorobenzene and 3-nitropyridine with molar ratios of 1:1, 2:1, and 1:2, respectively, are prepared by slow evaporation methods. Powder X-ray diffraction experiments carried out on the 1:1 and 2:1 cocrystals confirm that gentle grinding does not alter the crystal forms. 1H → 13C and 19F →13C cross-polarization magic angle spinning (CP/MAS) NMR experiments performed on powdered samples of the 1:1 and 2:1 cocrystals are used as spectral editing tools to select for either the halogen bond acceptor or donor, respectively. I also describe the formation of a new cocrystal of 1, 3, 5-trifluoro-2, 4, 6-triiodobenzene and piperazine with a 2:1 molar ratio that was prepared by the slow evaporation method. In addition of that, I have prepared the cocrystal (1,4- VII diiodotetrafluorobenzene)(coumarin ) already reported. After preparation and purification process of this compound, I obtained a small amount powder, but could not characterize it by solid-state NMR; rather I performed powder X-ray diffraction to study this compound. Overall, this work contributes new examples to the field of polymorphism in halogen-bonded systems and to variable stoichiometry cocrystal engineering with halogen bonds.

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.