Construction And Properties Of Metal-Organic Frameworks With S- Or P-block Metals

Metal-organic frameworks（MOFs） have emerged as a new class of crystalline porous solid with designed, adjustable, and modifiable structures, which have potential applications in diverse areas including gas storage/separation, recognition of organic molecular, catalysis, smart molecular device, and so on. So far, abundant MOFs have been reported, among which the examples with divalent d-block metals and trivalent f-block lanthanides are well known. In contrast, MOFs based on trivalent s- and p-block metals are relatively scarce. In comparison with d- and f-block metals, s-block metals(Li⁺, Na⁺, Mg²⁺, and Ca²⁺ ions) have lighter molar mass and can effectively increase the gas adsorbing capacity per unit mass, while the trivalent p-block metals(for example Al³⁺ ion) have been illustrated to be the promising candidates for constructing various coordination frameworks with high physicochemical stability. This thesis reports a series of MOFs based on C₃ symmetry tricarboxylate ligands and s-/p-block metals(Li⁺, Na⁺, Mg²⁺, Ca²⁺, and Al³⁺ ions). Based on the detailed structural characterization, we study their physicochemical stability, gas adsorption, fluorescence recognition upon small organic molecule, and organic dyes adsorption.In chapter 1: The backgrounds of this thesis and current research focuses on MOFs are introduced. Some works relating to synthetic strategy, synthetic methods, crystal/topological structures, and properties of MOFs based on s-/p- block metals. The aim and progress of this work is also outlined.In chapter 2: We obtained three new microporous Al-MOFs（467-, 515-, and 516-MOF） by using a series of flexible tricarboxylate ligands with C₃ symmetry. We overcame the synthetic challenge of Al-MOFs and successfully got their single crystals that are suitable for X-ray single crystal diffraction. Three Al-MOFs all exhibit highly thermal and chemical stabilities, CO₂ sorption selectivity, and fluorescence recognition upon small organic molecule.In chapter 3: By employing a series of C₃ symmetry tricarboxylate ligands with different ring skeletons, we get nine new MOFs based on s-block metal ions. 489-MOF can impregnates Eu³⁺ and Tb³⁺ ions into its channels resulting in adjustable light-emitting behaviors. 472-MOF shows both high thermal and chemical stability and good gas adsorption properties. 511-MOF has 1D circular microporous channels and octahedral microporous cages base on a rare Na₉ SBU, which is good at selective adsorption of different dye molecules. Additionally, 465-MOF and 472-MOF exhibit nice sorption capability for organic solvents, interesting guest-dependent luminescent properties, and the detection of nitrobenzene explosives.