Metal-Organic Frameworks (MOFs) are hybrid materials and are acknowledged as an important class of functional solid-state materials with high scientific interest in academia and industry alike. Their modular nature in terms of structural and compositional diversity, tunability, high surface area, and controlled pore size renders MOFs as the ideal candidate to address various persistent challenges pertaining to gas storage/separation, catalysis, drug delivery, and smart sensing. Through the field of reticular chemistry, targeted structures can be constructed through multiple design approaches, based on preselected building blocks prior to the assembly process. This thesis illustrates the merit of the supermolecular building layer (SBL) approach for the rational construction and discovery of highly connected and porous MOFs based on rare earth cations. Specifically, the emphasis of this study is on (i) the rational design and synthesis of 3-periodic MOFs based on SBLs pillared by ditopic ligands through post-synthetic modification (PSM) and in situ reactions. (ii) The investigation of the mixed-ligand system with different lengths and geometry of ditopic ligands on the isolation of metal clusters with distinct pore sizes. (iii) Gaining an overall insight into the exploration of different synthetic pathways that control the assembly of rare earth MOFs.

Metal-Organic Materials (MOMs) represent an important class of solid-state crystalline materials. Their countless attractive attributes make them uniquely suited to potentially resolve many present and future utilitarian societal challenges ranging from energy and the environment, all the way to include biology and medicine. Since the birth of coordination chemistry, the self-assembly of organic molecules with metal ions has produced a plethora of simple and complex architectures, many of which possess diverse pore and channel systems in a periodic array. In its infancy however this field was primarily fueled by burgeoning serendipitous discoveries, with no regard to a rational design approach to synthesis. In the late 1980s, the field was transformed when the potential for design was introduced through the seminal studies conducted by Hoskins and Robson who transcended the pivotal works of Wells into the experimental regime. The construction of MOMs using metal-ligand directed assembly is often regarded as the origin of the molecular building block (MBB) approach, a rational design strategy that focuses on the self-assembly of pre-designed MBBs having desired shapes and geometries to generate structures with intended topologies by exploiting the diverse coordination modes and geometries afforded by metal ions and organic molecules. The evolution of the MBB approach has witnessed tremendous breakthroughs in terms of scale and porosity by simply replacing single metal ions with more rigid inorganic metal clusters whilst preserving the inherent modularity and essential geometrical attributes needed to construct target networks for desired applications. The work presented in this dissertation focuses upon the rational design and synthesis of a diverse collection of open frameworks constructed from pre-fabricated rigid inorganic MBBs (i.e. [M(CO2)4], [M2(RCO2)4], [M3O(RCO2)6], MN3O3, etc), supermolecular building blocks (SBBs) and 3-, 4- and 6-connected organic MBBs. A systematic evaluation concerning the effect of various structural parameters (i.e. pore size and shape, metal ion, charge, etc) on hydrogen uptake and the relative binding affinity of H2-MOF interactions for selected systems is provided.

Porous solids are a class of materials of high scientific and technological significance. Indeed, they have the ability to interact with atoms, ions or molecules not only at their surface but also throughout the bulk of the solid. This ability places these materials as a major class involved in many applications such as gas storage and separation, catalysis, drug delivery and sensor technology. Metal-Organic Materials (MOMs) or coordination polymers (CPs) are crystalline compounds constructed from metal ions or clusters and organic components that are linked via coordination bonds to form zero-, one-, two or three-periodic structures. Porous Metal-Organic Materials (MOMs) or Metal-Organic Frameworks (MOFs) are a relatively new class of nanoporous materials that typically possess regular micropores stable upon removal of guests. An extraordinary academic and industrial interests was witnessed over the past two decades and is evidenced by a fantastic grow of these new materials. Indeed, due to a self-assembly process and readily available metals and organic linkers, an almost infinite number of materials can, in principle, be synthesized. However, a rational design is very challenging but not impossible. In theory, MOMs could be designed and synthesized with tuned functionalities toward specific properties that will determine their potential applications. The present research involves the design and synthesis of functional porous Metal-Organic Materials that can be used as platforms for specific studies related to many applications such as for example gas storage and particularly hydrogen storage. In this manuscript, I will discuss the studies performed on existing major Metal-Organic Frameworks, namely Zeolite-like Metal-Organic Frameworks (ZMOFs) that were designed and synthesized in my research group. My research was also focused on the design and the synthesis of new highly porous isoreticular materials based on Metal-Organic Polyhedra (MOP) where desirable functionality and unique features can be introduced in the final material prior and/or after the assembly process. The use of hetero-functional ligands for a rational design toward binary or ternary net will also be discussed in this dissertation.

The modular nature of metal−organic materials allows for tuning their properties to meet a specific application through careful design of the molecular precursors, i.e. information encoding at the molecular level. Research in this area is highly interdisciplinary where synthetic organic chemistry, in silico modeling, and various analytical techniques merge together to afford better understanding of the basic science involved and eventually to result in enhanced control over the properties of targeted materials.

Uma nova série de metaloporfirinas supermoleculares não-planares foi obtida por meio de automontagem coordenativa de meso tetra(3-piridil)porfirinas e complexos de rutênio polipiridina ([Ru(bipy)2Cl]+ e [Ru(bipy)2(OH2)]2+). Suas propriedades estruturais e eletrônicas foram investigadas por espectroscopia eletrônica, espectrometria de massas, voltametria cíclica e espectroeletroquímica. As influências do acoplamento eletrônico e da mudança da geometria molecular também foram avaliados, tanto no estado gasoso quanto em solução, e os resultados, comparados com a série de isômeros planares obtidos através da coordenação de complexos de rutênio polipiridina as meso tetra(4-piridil)porfirinas. Nanomateriais eletrostaticamente montados, camada por camada, com derivados aniônicos de porfirinas e ftalocianinas foram elaborados. As propriedades eletrocatalíticas dos mesmos foram investigadas, frente a substratos de interesse como nitrito e sulfito. Efeitos supramoleculares conformacionais e eletrônicos foram observados, tanto em solução quanto nos filmes dos nanomateriais porfirínicos supramoleculares. Verificou-se também, uma influência significativa do pH e do íon metálico coordenado à porfirina nos processos de oxidação e de redução de nitrito e de sulfito. / A new series of nonplanar supermolecular metalloporphyrins have been obtained by coordenative self-assembly of meso-tetra(3-pyridyl)porphyrins and ruthenium complexes such as [Ru(bipy)2Cl]+ and [Ru(bipy)2(OH2)]2+. The electronic and structural properties have been investigated by electronic spectroscopy, mass spectrometry, cyclic voltammetry, and spectroelectrochemistry. The effects of the electronic coupling and molecular geometry on the molecular and nanomaterials properties were investigated in the gas phase and in solution. All results were compared with that obtained for the planar isomers obtained by the coordination of four [Ru(bipy)2Cl] groups to the meso-tetra(4-pyridyl)porphyrins. New nanomaterials were obtained by layer-by-layer electrostatic assembly of those supermolecular cationic porphyrins and tetrasulfonated porphyrins or phthalocyanines. The electrocatalytic properties were investigated for nitrite and sulfite. Electronic and supramolecular conformational effects were observed for those species in solution and in films of the nanomaterials. Moreover, a significant effect of the pH and of the transition metal ion coordinated to the porphyrin ring on the electrocatalytic activity were also observed.

Uma nova série de metaloporfirinas supermoleculares não-planares foi obtida por meio de automontagem coordenativa de meso tetra(3-piridil)porfirinas e complexos de rutênio polipiridina ([Ru(bipy)2Cl]+ e [Ru(bipy)2(OH2)]2+). Suas propriedades estruturais e eletrônicas foram investigadas por espectroscopia eletrônica, espectrometria de massas, voltametria cíclica e espectroeletroquímica. As influências do acoplamento eletrônico e da mudança da geometria molecular também foram avaliados, tanto no estado gasoso quanto em solução, e os resultados, comparados com a série de isômeros planares obtidos através da coordenação de complexos de rutênio polipiridina as meso tetra(4-piridil)porfirinas. Nanomateriais eletrostaticamente montados, camada por camada, com derivados aniônicos de porfirinas e ftalocianinas foram elaborados. As propriedades eletrocatalíticas dos mesmos foram investigadas, frente a substratos de interesse como nitrito e sulfito. Efeitos supramoleculares conformacionais e eletrônicos foram observados, tanto em solução quanto nos filmes dos nanomateriais porfirínicos supramoleculares. Verificou-se também, uma influência significativa do pH e do íon metálico coordenado à porfirina nos processos de oxidação e de redução de nitrito e de sulfito. / A new series of nonplanar supermolecular metalloporphyrins have been obtained by coordenative self-assembly of meso-tetra(3-pyridyl)porphyrins and ruthenium complexes such as [Ru(bipy)2Cl]+ and [Ru(bipy)2(OH2)]2+. The electronic and structural properties have been investigated by electronic spectroscopy, mass spectrometry, cyclic voltammetry, and spectroelectrochemistry. The effects of the electronic coupling and molecular geometry on the molecular and nanomaterials properties were investigated in the gas phase and in solution. All results were compared with that obtained for the planar isomers obtained by the coordination of four [Ru(bipy)2Cl] groups to the meso-tetra(4-pyridyl)porphyrins. New nanomaterials were obtained by layer-by-layer electrostatic assembly of those supermolecular cationic porphyrins and tetrasulfonated porphyrins or phthalocyanines. The electrocatalytic properties were investigated for nitrite and sulfite. Electronic and supramolecular conformational effects were observed for those species in solution and in films of the nanomaterials. Moreover, a significant effect of the pH and of the transition metal ion coordinated to the porphyrin ring on the electrocatalytic activity were also observed.

Two new mesoporous metal–organic frameworks (DUT-75 and DUT-76) with exceptional ethene uptake were obtained using carbazole dicarboxylate based metal–organic polyhedra as supermolecular building blocks. The compounds have a total pore volume of 1.84 and 3.25 cm³ gˉ¹ and a specific BET surface area of 4081 and 6344 m² gˉ¹, respectively, and high gas uptake at room temperature and high pressure.

No description available.

No description available.

Depuis 1973, l’un des objectifs principaux de la France est la diminution de la consommation des énergies de chauffage des bâtiments du résidentiel et du tertiaire qui représentent plus de 40% de la consommation énergétique totale du pays. Le développement des isolants thermiques a été par conséquent un sujet de recherche qui a abouti à de nouveaux matériaux : les super-isolants thermiques de conductivité thermique inférieure à 25 mW.m-1.K-1. Les aérogels organiques de faible densité de Z-Phe-NH-Napht étudiés au LCPM présentent une structure fibrillaire qui leur confère des propriétés thermiques intéressantes malgré une résistance mécanique faible. Une étude fondamentale de l’organisation supramoléculaire nous a permis d’une part de démontrer l’existence de deux modes d’empilement des molécules organogélatrices : tête-à-tête (monocristaux) et tête-à-queue (gels), caractérisées par une signature infrarouge propre à des pseudo-cycles respectivement en C12 et C10/C14. D’autre part, nous avons étudié le mécanisme de formation séquentiel de ces gels et abouti à un modèle complet d’organisation de la molécule isolée à la fibre basé sur une symétrie hexagonale. En vue d’une commercialisation d’un isolant à base d’aérogel organique, nous avons tout d’abord optimisé le protocole d’obtention des aérogels pour ensuite travailler à l’amélioration des propriétés thermiques et mécaniques. Nous sommes parvenus à un nouvel isolant hydrophobe présentant une conductivité thermique de l’ordre de celles des super-isolants et de bonnes propriétés mécaniques compatibles avec les pré-requis industriels pour une application dans le bâtiment / Since 1973, France's main objective in this domain has been to reduce the consumption of energy in heating residential and industrial buildings, which represents more than 40% of the national consumption. Consequently, the development of heat insulators has been the subject of research which has resulted in new materials: super thermal insulators with a thermal conductivity of less than 25 mW.m-1.K-1. Organic aerogels with a low density of Z-Phe-NH-Napht have been studied at LCPM for the past 10 years. Despite their very weak mechanical resistance they present a fibrillar structure which gives them very interesting thermal properties. A fundamental study of the supermolecular self-assembly allowed us to demonstrate the existence of two stacking methods of gelling molecules: head-to-head (monocrystals) and head-to-tail (gels) which are characterized by a specific infrared signature to the pseudo-cycles respectively on C12 and C10/C14. In addition, we also studied the sequential formation mechanism of these gels which resulted in a full model of their molecular organization from the single molecule to the fiber and based on a hexagonal packing symmetry. In aim of commercializing an insulator made from organic aerogels, we firstly optimized the protocol for obtaining aerogels to then work on improving their thermal and mechanical properties. We created a new hydrophobic insulator which has both a thermal conductivity in the range of the super heat insulators' and good mechanical properties that are compatible with industrial prerequisites for the construction of buildings