Syntheses And Properties Of Metal-carboxylate Coordination Polymers

Due to their diverse topological structure,coordination polymers have potential applications in gas adsorption and separation,optics,electronics,chiral separation and catalysis.Remarkable attention has been received not only from the self-assembly of a specific metal-carboxylate coordination polymers using carboxylate ligands and metal ions but also from their applications in related fields.In this paper,we have adopted two kinds of ligands:rigid bicarboxylic acid ligand1,4-H₂NDC,semi-rigid carboxylic acid 5-Aminoisophthalic Acid with ds metal ions（Cd,Cu）to synthesize two kinds of metal coordination polymers.The structures and properties of these complexes have been investigated.The thesis was summarized from three chapters as follows:1.The development history,structures,applications of coordination polymers have been described.2.Two enantiomeric three dimensional chiral coordination polymers[Cd（NDC）（DMF）]_n（MCF 1_L and MCF 1_D）have been one-pot synthesized by introducing the rigid achiral bicarboxylic acid ligand under solvo-thermal condition,without chiral template or additives.Both chiral Cd-CPs were characterized by single-crystal X-ray crystallography,FT-IR,TGA,solid-state luminescent spectrum and powder X-ray diffraction.Structural analysis indicates that MCF 1_L and MCF 1_D are enantiomers based the zigzag[Cd（COO）]_n rod secondary building units,feature the left-or right-hand 2₁ Cd-O-C-O-helix chains and left-or right-hand 4₁ screw[Cd（NDC）]_n columns,respectively.It is intriguing that the evidence from the circular dichroism spectroscopes confirms enantiomeric excess in the whole spontaneous resolution crystallization.3.A semi-rigid angular tetra-carboxylic acid bearing carbonyl groups was used to self-assemble the metal organic framework[Cu₂₄（L）₁₂（H₂O）₂₄]_n·xGuest（MCF 2）,featuring a circuitous porous and free carbonyl decorated cages.MCF 2 exhibits high and intriguing two steps UO₂²⁺adsorption behaviour,ascribed to crystal surface-and inner-microcrystal processes.The latter is ascribed to the cooperative interplay of the circuitous porous host framework and the free carbonyl coordination sites,as witnessed by a red-shift of the infrared[O=U^VI=O]²⁺antisymmetric vibration band.After 5 regeneration cycles,MCF 2 exhibits a sorption capacity as high as 520 mg/g.