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 design of functional materials for specific applications has been an ongoing challenge for scientists aiming to resolve present and future societal needs. A burgeoning interest was awarded to developing methods for the design and synthesis of hybrid materials, which encompass superior functionality via their multi-component system. In this context, Metal-Organic Materials (MOMs) are nominated as a new generation of crystalline solid-state materials, proven to provide attractive features in terms of tunability and versatility in the synthesis process. In strong correlation with their structure, their functions are related to numerous attractive features, with emphasis on gas storage related applications. Throughout the past decade, several design approaches have been systematically developed for the synthesis of MOMs. Their construction from building blocks has facilitated the process of rational design and has set necessary conditions for the assembly of intended networks. Herein, the focus is on utilizing the single-metal-ion based Molecular Building Block (MBB) approach to construct frameworks assembled from predetermined MBBs of the type MNx(CO2)y. These MBBs are derived from multifunctional organic ligands that have at least one N- and O- heterochelate function and which possess the capability to fully saturate the coordination sphere of a single-metal-ion (of 6- or higher coordination number), ensuring rigidity and directionality in the resulting MBBs. Ultimately, the target is on deriving rigid and directional MBBs that can be regarded as Tetrahedral Building Units (TBUs), which in conjunction with appropriate heterofunctional angular ligands are capable to facilitate the construction of Zeolite-like Metal-Organic Frameworks (ZMOFs). ZMOFs represent a unique subset of MOMs, particularly attractive due to their potential for numerous applications, arising from their fully exploitable large and extra-large cavities. The research studies highlighted in this dissertation will probe the validity and versatility of the single-metal-ion-based MBB approach to generate a repertoire of intended MOMs, ZMOFs, as well as novel functional materials constructed from heterochelating bridging ligands. Emphasis will be put on investigating the structure-function relationship in MOMs synthesized via this approach; hydrogen and CO2 sorption studies, ion exchange, guest sensing, encapsulation of molecules, and magnetic measurements will be evaluated.