Green Synthesis Approach to Coordination Polymers by Mechanochemistry

The field of Metal-Organic Frameworks, also known with the abbreviation MOFs, has been subjected to an accelerated growth in the last 15 years. The process of mixing quickly available metal precursors with organic ligands—many of which are commercially available—to produce a wide range of frameworks, is capturing the interest of chemists and materials scientists worldwide. There is an important link between MOF chemistry and fields of inorganic and coordination chemistry, there is also a conceptual link into the field of materials chemistry that has evolved applications ranging from catalysis to energy storage. Organic chemistry is also able to contribute to the MOFs design by the synthesis of new ligands with the aim of giving different properties to the MOF wall. X-ray crystallography and solid-state chemistry provide information about the structures of MOFs so that the process of designing and synthesizing MOFs can be refined to control a targeted property of those frameworks. My PhD thesis aims to explore, especially from the point of view of synthetic and structural, morphological, thermal and textural characterizations, the chemistry of Coordination Polymers (CPs) and Metal-Organic Frameworks (MOFs). Mechanochemical synthesis has been adopted as a powerful method for environmentally-friendly CPs and MOFs synthesis. The experimental section, have been divided in four parts: the first part concerns the efficient mechanosynthesis of an iron(III) trimesate MOF and its usage for the adsorption of 4,6-dimethyldibenzothiophene (4,6-DMDBT) from a simulated low-sulfur diesel fuel. In the second, the structural, thermal and morphological properties of CPs based on unsatured Ni(II) dithiophostato/ dithiophospnonato complexes and 4,4’-bipyridine as linker are outlined. The third part dials with an array study of reactivity under mechanochemical conditions of a set of CPs based on the same unsatured Ni(II) complexes with different topologies of polydentate ligands. The final part is dedicated to the attempt to obtain thio-functionalized ligands for design, synthesis and future application in CP/ MOF architecture.