Design, Syntheses, Structure And Properties Of Coordination Polymer Constructed Through Several Ligands Including Polycarboxyl Group (tp,btec,H₂IDA,dcbp)

Recently, coordination polymers and supramolecular architecturesformed through the deliberate selection of metals and multifunctionalligands have received much attention for their fascinating structuraldiversity and specific functionality, which have made them highlypromising in various applications, particularly absorption, catalysis andmolecular magnetization. According to the principle of crystal engineering,it is possible that rational design and synthesis of porous crystallinematerials by selecting certain geometric metal ions and special organicligands. The design and synthesis of materials with helical structures aretopics of current interest and of great challenge. Helical structures are oftenfound in nature, but are rare in synthetic materials. In recent years, thedesign of helical coordination polymers through the self-assembly of theligands and metal cations has achieved much progress, but most of themare prepared in phosphates, phosphates and oxides under hyderthermalconditions in the presence of organic amine as a structure-directing agent(template). The aim of this work is to construct the coordination polymerthrough diverse ligands including dicarboxyl or polycarboxyl groups(terephthalate, 1,2,4,5-benzenetetracarboxylate, iminodiacetic acid,4,4'-dicarboxy-2,2'-bipyridine, 3,3'-dicarboxy-2,2'-bipyridine) using theself-assembly and hydrothermal reaction. This dissertation is divided intofive parts. Firstly one briefly introduce about the concept and development ofcoordination polymers are given, as well as the current survey, researchsignificance, reviews on the coordination polymers constructed fromligands including carboxyl group and the general syntheses method. Two rigid aroma polycarboxyl ligands have been introduced into the iiicomplexes. A Zn(II) complex 1 and a one-dimensional polymeric Cd(II)complex 2 constructed with terephthalate in the presence of an additionalchelate ligand 2,2'-bipyridine have been described in different PH value,and the fluorescent properties are given. In general, d10 metal, such asZn(II), Cd(II) Cu(I) and Ag(I), complexes give strange photoluminescentphenomena. At the same time one three-dimensional coordination polymer{[Cd2(btec)(H2O)2]·[(H2O)0.25]2}n 3 have been obtained bridging in1,2,4,5-benzenetetracarboxylate, and there are channels in the structure inwhich the H2O molecules reside. Complex 3 gives good fluorescentproperties, too. Amino acid is a kind of well-exploited ligand and it has morecoordinated sites, so it is of great interest in biochemistry and other fields.Iminodiacetic acid is good ligand and well used for the system of thelanthanide-transition metal, especially lanthanide-Cu(II) which thestructures and the magnetism is studied. But till now no lanthanide-Zn(II)complex is reported. Here a flexible ligand "iminodiacetic acid" was usedfor bridge ligand to form complex. In the present of the Phen the ligandcoordinated to Cu(II) to form a independent complex 4, and the spetrastudies have been carried out in experimental and theoretical method. Inaddition, two two-dimensional coordination polymers 5 and 6 have beengot in the condition of the existing of the transition metal Zn2+ andlanthanide La3+ or Nd3+ in which the ligand iminodiacetic acid shows twokinds of coordination mode, one is chelated to the transition metal Zn2+,and the other is as a helical mode to bridging the La3+ or Nd3+. Two types of dicarboxy-2,2'-bipyridine ligands, 4,4'-dicarboxy-2,2'-bipyridine (4,4'-dcbp) and 3,3'-dicarboxy-2,2'-bipyridine (3,3'-dcbp) areacting as ligands to coordinate to main group metal Pb(II), and at longintervals the second ligand 4,4'-bipyridine is put into the system. Totallyfour different structures are obtained in diverse conditions. In terms of the3,3'-dicarboxy-2,2'-bipyridine ligand, it often gives helical conformationbecause of the steric hindrance, thus it can br...