Synthesis And Properties Of Luminescence Of The Metal Organic Frameworks

In recent years, Metal Organic Frameworks(MOFs) is a new type of solid materials received extensive attention, which has potential applications in catalysis, sensing,fluorescent, drug delivery, gas adsorption and separation. So far, thousands of luminescence of MOFs was reported, and the luminescence can exist in several forms, including direct organic ligands excitation, metal–centered emission, LMCT, MLCT, and guest molecules onto MOFs can also result in luminescence. And research on luminescence sensor by MOFs also has a lot of potential application. We started choose some luminescence ligand to build MOFs with luminescence properties and research on potential applications of chemical sensor.In the second chapter, we reported the synthesis and characterization of two MOFs Zn(IN)2(compound 1) and Zn(IN)2(HNO3)(H2O)(compound 2) using ligand isonicotinic acid.Compound 1 is a framework isomer of the reported compound Zn(IN)22H2O with 3-fold interpenetrating networks. They have the same coordination environment, but different interpenetrating networks, as result there are many different properties between them, like color, space group and especially optical properties. Compound 2 is a 1D chain MOFs with a similar structure as reported. And there was process of crystal phase transformation at 100℃for 2.In the third chapter, we reported the synthesis and structures of three metal–organic coordination polymers of m-phenylenediacrylate acid(mpda) with metalions(Zn, Pr,Mn)formulated as [Zn(mpda)(H2O)](compound 3), [Pr2(mpda)2(H2O)2(CHOO)2](compound 4),and [Mn2(mpda)2(H2O)4](compound 5). These three metal organic frameworks exhibit 2D,3D, and 1D structures, respectively. Furthermore, characterization of compound 3, 4, and 5was investigated. In addition, because compound 4 and reported sample[Nd2(mpda)2(H2O)2(CHOO)2](compound 4’) are isomorphous MOFs, and their synthetic methods are basically the same, the mixed sample[Nd(mpda)(H2O)(CHOO)Pr(mpda)(H2O)(CHOO)](compound 4’’) has been synthesized and studied. Finally, we studied the fluorescence sensing performance of these compounds to solvent and metalions. Compounds 3 and 4 exhibit a selective sensing function respect to acetone, Zn2+ and Ni2+. It was also found that compound 3 could act as two fluorescent logicgates operated by two chemical inputs(Fe3+ and Zn2+, Bi2+ and Zn2+).In the fourth chapter, we reported the synthesis of seven MOFs using semi-rigid ligand5–(2’,3’–Dicarboxylphenoxy)isophthalic acid(HDIA): Cd2(C16H8O9)2(H2O)7(compound 6),Co(C16H9O9)2(H2O)8(compound 7),Pr(C16H7O9)(H2O)2(compound 8),Er(C16H7O9)(H2O)4(compound 9), Ag6(C16H6O9)2(compound 10), Zn(C16H9O9)2(H2O)8(compound 11),Y(C16H8.5O9)2(H2O)7(compound 12). These compounds exhibit 0D, 1D, 2D and 3D structures,in addition the characterization including X–ray Diffraction, XRD, IR, TG and fluorescence.In the fifth chapter, we synthesised three metal organic frameworks: yellow compound Cd(pyba)(compound 13) using ligand 2–(Pyridin–3–yloxy)–benzoic acid(H2pyba) and Cd(NO3)2, Ag2(pca)(NO3)(compound 14) using ligand pyrazine–2–carboxylic acid(Hpca)and Ag NO3, green compound Pr(C5.5H3O7S)(H2O)4(compound 15) using ligand5-sulfoisophthalic acid(SPA) and Pr Cl3. in addition the characterization including X-ray Diffraction, XRD, IR, TG and fluorescence were carried out.The sixth chapter, three extened large polar and fluorescent ligands including 2,5–di(4–pyridyl) thiazolyl[5,4–d] thiazole(ligand 1), 2,6- Di(4–carboxystyryl)Pyridine(ligand 2), 2,5–di(4–carboxylstyryl)pyrazine(ligand 3) have been synthesized. And used them to try the synthesis of MOFs, the results show that the ligand 1 more easily formed a ligand crystal precipitation, had not obtained metal complexes. Ligand 2 and 3 in methanol under the addition of metal salts obtained crystal of formate of ligand, the results show that the esterification catalytic effect of metal salts.