Syntheses、Structures And Property Studies Of New Coordination Polymers With O-、N-containing Ligands

The aim of this thesis is to synthesize new coodination polymers on the basis of organic N-or O-donor ligands and metal ions or multi-nuclear metal-oxygen clusters under hydrothermal conditions, to study the synthetic conditions and rules for these compounds, analysis influence of structures of organic ligands, metal salts and polyoxometalates on the formation of ultimate structures, and to explore the relationships between structures and properties for these new compounds.1> Six new coordination compounds are synthesized on the basis of two kinds of rigid N-heterocyclic multi-carboxylate ligands2-(pyridine-4-yl)-1H-imidazole-4,5-dicarboxylic acid (p-H3PIDC) and2-(pyridine-2-yl)-1H-imidazole-4,5-dicarboxylic acid (o-H3PIDC) as organic ligands.[(Cu2(o-HPIDC)2(H2O)2]n (1)[Cu(o-HPIDC)(phen)(H2O)]n (2)[(Cu(o-HPIDC)(bpy)(H2O)·2H2O]n (3){[Cu(o-H2PIDC)(phen)Cl]·[Cu(phen)2Cl]·10H2O·Cl}n (4){[(Mn4(o-HPIDC)4(phen)4]·0.5(phen)}n (5){[Nd(p-HPIDC)(ox)0.5(H2O)]·2H2O}n (6)The non-covalent interactions play important role for constructing and stabilizing the3D supramolecular structures of compounds1-5.Compounds1and5are the one-dimensional (ID) infinite chains. Compounds2-4show zero-dimensional (OD) mononuclear molecule structures, which are stabilized into three-dimensional (3D) supramolecular architectures through hydrogen bonds and π…π stacking interactions. Notably, in compound4there is a two-dimensional (2D) water-chloride anionic layer formed by hydrogen bonds among the minimal repeating{[(H20)20(Cl)2]2-}n fragments. In compound6, ox2-ligands link the2D [Nd(p-HPIDC)]n layers into a (4·82)(4·85)3D network structure with two pairs of single-left (L) and single-right-handed (R) helical chains.2、Three organic-inorganic hybrid compounds are synthesized based on the classical Keggin type polyoxometalate anion [SiMo12O40]4-(SiMo12) as basic building blocks and different kinds of flexible bis(triazole) ligands with different length and transition metal CuⅡ.[Cu(bte)(H2O)]2·SiMo12O40·2H2O (7)[Cu(btb)2(H2O)]2·SiMo12O40(8)[Cu(btb0.5)4]2·SiMo12O40·2H2O (9) In compound7, these cationic grid sheets, connected by Cu-1,2-bis(1,2,4-triazol-1-yl)ethane (bte) complexes, are paired and parallel with each other, between which the [SiMo12O40]4-anions are sandwiched to form a layer unit through hydrogen bonds. Under the same reaction, compounds8and9were synthesized with two different structures. Compounds8exhibits a2D double-layer structure connected by Cu-1,4-bis(1,2,4-triazol-1-yl)butane)(btb) complex, in which [SiMo12O40]4-anions are inserted. Compounds9exhibits a3D Cu-btb framework with hexanuclear metal channels, into which the tetradentate [SiMo12O40]4-anions are incorporated.