| Organic metal frame materials (MOFs) are a new type of porous materials, which are composed by central metal atoms and organic ligands. Through the design of organic ligand and the choice of metal ions, coordination polymers with different topology structure and properties could be built. This makes this sort of polymer compounds have potential applications in biological activity, medicine, optical materials, catalysis, adsorption, gas storage aspects.Based on the purpose of obtaining several kinds of material with big pores, eight v-type frame structure ligands were designed and synthesized: (1) 9,9′-Bis(4-carboxylic acid phenyl) fluorine (L1); (2) 1,1′-Bis(4-carboxylic acid phenyl) cyclohexane (L1′); (3) 9,9′-Bis (4-1-H-tetrazylphenyl) fluorine (L2); (4) 9,9′-Bis(4-phosphoric acid phenyl) fluorine (L3); (5) 1,1′-Bis(4-phosphoric acid phenyl) cyclohexane (L3′); (6) 9,9′-Bis(4-1-imidazolyl phenyl) fluorine(L4); (7) 9,9′-Bis(4-1,2,3-triazolylphenyl)fluorine(L5); (8) 9,9′-Bis (4-1,2,4-triazolyl phenyl) fluorene. For every kind of ligands were characterized by NMR.In this article, through solvent hot method, by using ligand L1 and ligand L1? with three metal salt of Zn(NO3)2·6H2O, Cu(NO3)2·3H2O, Co(NO3)2·6H2O. Five coordination polymers were produced: (1) [Cu(L1)(DMF)]n; (2) [Zn(L1)(H2O)]n; (3) [Co(L1)(DMF)]n; (4) [Cu(L1′)(DEF)]n; (5) [Zn(L1′)(DMF)]n. In these complexes, complexes (1)3 were produced by the ligand L1, and complexes (4)?(5) were produced by ligand L1?, the optimal synthetic route was discovered after the reaction condition was investigated.The optimal synthetic route of coordination polymer (1) was followed: 1 molar ratio of L1 and Cu (NO3)2·3H)2O. DMF and CH3OH were used as the solvents, the volume ratio of them was 1:1, reaction temperature was 115℃, time was four days. Then obtained the blue block crystal, the yield was 41.1%.The optimal synthetic route of coordination polymer (2) and (3) were followed: 3 molar ratio of L1 and Zn(NO3)2·6H2O or L1 and Co(NO3)2·6H2O. DMF were used as the solvents, reaction temperature was 90℃, time was three days. Then obtained the colorless transparent crystal and dark green crystals, the yields were 51.3 % (complexes (2)) and about 100 % (complexes (3)).The optimal synthetic route of coordination polymer (4) was followed: 3 molar ratio of L1? and Cu(NO3)2?3H2O. DEF and H2O were used as the solvents, the volume ratio of them is 3:1,reaction temperature was 90℃, time was three days. Then obtained the blue cone crystals, the yield was 45%.The optimal synthetic route of coordination polymer (5) was followed: 3 molar ratio of L1? and Zn(NO3)2?6H2O. DMF were used as the solvents, reaction temperature was 90℃, time was three days. Then we obtained the colorless transparent crystals. The yield was 69%.All of the five coordination polymers were investigated by XRD and thermogravimetric analysis (TGA) technology.By analyzing these five kinds of complexes coordination environment and space accumulation patterns, we knew that: In these five kinds of the coordination polymers, complexes (1) (4) have the same coordination model, the coordination number of the metal ions was six, which belonged to distorted octahedron mode, the carboxylic acid root of ligands took the model of cis-cis bidental. the coordination number of the metal ion of complexes (5) was five, the carboxylic acid root of ligands took the model of tris-tris bidental and chelating patterns. From the packing diagrams of the five complexes. we can see that the complexes (1) (3) formed the two-dimensional structure, in which the ligand exsisted the left spiral and right spiral structure. and one-dimensional chain structure was formed by the complexes (4) and (5), in which only simple hole existed.From the thermo gravimetric analysis results, we knew that two phases of weight loss were happened, coordination polymer (1): 261.8℃?386℃(DMF lost), 386℃?595℃(structure collapsed); coordination polymer (2): 125℃?211℃(H2O lost), 211℃?500℃(structure collapsed); polymer (3): 180℃?311℃(DMF lost) 311℃?505℃(structure collapsed); polymer (4): 227℃?267℃(DEF lost), 267℃?511℃(structure collapsed); polymer (5):186℃?276℃(DMF lost), 276℃?530℃( structure collapsed). From the data, we could see that the complexes (1) and (3) with two-dimensional structure in space had more thermal stability than the complexes (4) and (5) with one-dimensional structure. The destruction temperature of structure of complexes (1) and (3) was above 300℃; however the destruction temperature of structure of complexes (4) and (5) was from 250℃to 300℃. Although coordination polymers (2) also had two-dimensional structure, the water molecules existed in the structural frame. Which led to a lower temperature of water lost and structure collapse than the complexes (1) and (3).
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