Design, Synthesis And Properties Of Metal Organic Frame Materials Based On Carboxylic Acid Bridged Ligands

Metal-organic frameworks are of great interest for their excellent physical andchemical properties and become one of the important issues of inorganic chemistry,analytical chemistry and life sciences, etc. Under the guidance of the crystalengineering, it has been rasied considerable concern about synthesizing metal-organicframework materials with outstanding properties by metal ions and organic bridgingligands. Carboxylate ligands with strong coordination ability and flexibility incoordination mode, has been widely used to synthesize metal organic frameworkmaterials. This thesis presents the synthesis of5,10,15,20-Tetra(4-carboxyphenyl)porphyrin,5-(1-carboxyethoxy)isophthalic acidand [1,1’,2’,1’’-terphenyl]-3,3’’-dicarboxylic acid. By introduction of different endgroup or neutral bridging ligands, a series of new metal-organic framework withdifferent metal ions are obtained. The characterization and some properties of crystalswere investigated by single-crystal structure determination, thermal gravimetricanalysis, UV-Vis, fluorescence imaging and catalytic experiment. The main resultscan be summarized as following:Ⅰ With5,10,15,20-Tetra(4-carboxyphenyl)porphyrin as ligand, a3D porous metalorganic framework {CuL[AlOH]2}nhas been synthesized and carried outbasic characterization. Then this mixed metal compound was used as a newprobe for the detection of gaseous signal molecule H2S in physiologicalenvironments. This is the first case for the detection of H2S in biologicalsamples by metal organic framework materials. At the same time, the confocalfluorescence imaging in living cells has also been realized.Ⅱ With5-(1-carboxyethoxy)isophthalic acid as chiral bridging ligand L1, fivemetal organic frameworks{[Ni4(L1)2(OH)2(H2O)4]·4H2O}n(1),{[Zn2(L1)2bpy]·0.5(H2O)}n(2),[Cd3(L1)2(bpy)2.5(H2O)2]n(3),{[Mn3(L1)2(bpy)3(H2O)3]·6(H2O)}n(4) and {[Co(L1)phen]·(H2O)}n(5) wereobtained and determine its crystal structure. Compounds1and2consist of2D coordination networks, while compound3and4present3D architecture. Byintroduction of end group ligands phenanthroline, the ligand sites ofcompound5are occupied by phenanthroline and only get a simpleone-dimensional linear chain which form three-dimensional supramolecularstructure by weak hydrogen bonds.Ⅲ With [1,1’,2’,1’’-terphenyl]-3,3’’-dicarboxylic acid as bridging ligand, other fournew coordination polymers [Zn(L3)(DMF)]n(6)、[Cu(L3)(DMF)]n(7)、{[Cd(L3)bpy]·3.5H2O}n(8) and {[Co(L3)bpy]·1.5H2O}n(9) have beenprepared. Single-crystal X-ray structural analysis revealed that all thesecompounds consist of2D coordination networks and form a three-dimensionalsupramolecular by the weak interaction between the layers. In addition tobasic structural characterization, photocatalysis of some coordinationpolymers were carried out.