Syntheses, Structures And Properties Of Metal-Organic Frameworks Based On Tetra-Carboxylate Ligand Functionalized With Amide Group

Metal-organic frameworks (MOFs) are porous crystalline solids thatconsist of metal centers connected to multi-dentate organic ligands via coordination bonds, forming repeating geometrical dimensions (OD (polygons and discrete polyhedra), 1D (chains, ladders and tapes),2D (sheets and bilayers), and 3D (extended networks with potential inner porosity)).The 3D extended networks of MOFs have uniform pore diameters (typically in the range 3 to 20 A) with unprecedented internal surface areas (even higher than 7000 m2·g-1 with the theoretical upper limit for MOF surface areas 14600 m2·g-1 (or greater)), high void volumes (55-90%), and low densities (0.21-1.00 g·cm-3).Their highly porous, modular nature and high thermal and chemical stabilities endows them with attractive properties, and their potential has been examined in many different areas such as gas storage, catalysis, sensing, separations, removal of hazardous materials, and light harvesting.1. This thesis is based on the four-carboxyl-contains ligand which includes amide group and different metals (mainly the main group metal Mg and transition metal Zn, Cu and Cd) form 18 complexes. These complexes are characterized by single X-ray crystaLdiffraction, IR, TG and PXRD, and some of these complexes are explored by gas storage, catalysis and light harvesting. The main work of the thesis is divided into three parts:1. MOFs material regulated by pH:Through solvent thermal method and different pH solvents, Mg and H4L form five different MOFs (1-5) by self-assembly, Reaching the target of regulationon porosity (1 to 3 to 4), and achieving a goal of two-dimensional structure 1 obtained from the acidic condition changing to a three-dimensional network structure 2,3 obtained from neutral conditions.2. Construction a series of two-dimensional planar structures by using auxiliary ligands:Zn and H4L form a two-dimensional plane structure 8 first, then by adding the auxiliary ligands containing pyridine group into the origin system, a series of MOFs complexes of two-dimensional structures (9-15) were obtained, including some isomorphi cheterogeneity (11-15), and we did research on their fluorescence properties.3. In this chapter, we obtained three three-dimensional structures of high porosity complexes (Cu-MOF (16), Cd-MOF (17) and In-MOF (18)) by adjusting the solvent system. We did research on heterogeneous catalysis, gas CO2 capture and selective separation research for complex 16 and adsorption of dyes experiment for the complexes 17,18.