Synthesis Of New Porous Metal-organic Framework Materials

In recent years, as a new type of porous functional materials, metal-organicframework (MOF) materials have been paid wide attention because of structurediversities, fanscinating properties as high specific surface area and highly porisity,and potential applications in adsorption, separation, catalytic, fluorescence, magnetic,drug delivery and biological imaging fields, and so on. The large pore size and highpore volume of MOFs may be accomplished by extending the arm chain of ligands,and the low framework densities of molecular seize may attain by triangular buildingblock units. In the thesis, we chose a kind of such ligand as1,3,5-benzenetricarboxylate holding a triangluar unit, and expected to prepare some MOFs withhighly porisity and low framework density. A series of ligand such as PTB and TBPMare synthesized, and their coordination polymers are observed. The full article wasdivided into five parts:In the first part, we simply outlined the concept, history and synthetic methodsof coordination polymers and what factor have key influence on the product expected.In addition, some potential applications in gas adsorption and separation, catalytic,fluorescence, magnetic properties of MOFs were beriefly presented. The interest andaim in this paper was introduced in this chapter.In the second part, a new ligand of2,4,6-tri-(4-carboxyphenyl) pyrimidine wassynthesized and its copper coordinaton polymer,[Cu3(TBPM)2(H2O)3]·2DMF·H2O,has been obtained. This coordination polymer holds a three-dimensional network withboracite topology and exhibits a large pore size of25.39×25.39. Some physicalproperties were characterized by x-ray powder diffraction (XRD), thermalgravimetric analysis (TGA) and N2sorption. N2sorption showed it possess a highspecific sureface aera of1763.939m2/gIn the third section, we obtained four coordination polymers by the reaction ofH3PTB with some inorganic salts such as cobalt nitrate, copper nitrate, zinc chlorideand cobalt chloride. Their physical properties were further characterized by XRD,TGA and variable—temperature magnetic susceptibility. The MOF of [Cu3(PTB)2(H2O)3]·3DMF·(C2H5OH)·H2O has one-dimensional hierarchicalchannels in the b axis including a hexagonal channel and square channel, which is27×11and11×11of size.The compound of [Co9(OH)6(PTB)4]·10DMF·3H2O isa three dimension network of being made up of Co6cluster building blockunits.[Co3O(PTBH)2]·8DMF and [Zn3O(PTB)2(DMF)2]2·6DMF has the identicalframework comprised of identail BBUs of M3cluster, which present1D squarelchannel along the a axis, respectively. The pore size was20×18and24×12.In the fourth part, three coordination polymers were obtained as the products ofH3BTC reacting with metal nitrate (metal=Zn(II), Co(II), Cd(II) and La(II)respectively. The coordination polymer of[ZnCo(BTC)(OH)(H2O)3]·NMP·DMF·1.5H2O possesses a (10,3)-a networkcomprised of heterodinuclear zinc-cobalt cluste and exhibits anti-ferromagnetism.The coordination polymer [Cd(BTCH)(DMF)2)]·(NMP) holds a (6,3) net. Thecoordination polymer of [La(BTC)(DMF)2] made up of dinuclear La2unit is athreedimensional network.Finally, we briefly summarize structural characteristics and selective physicalproperties of the eight synthesised coordination polymers...