2，2’-联吡啶-3，3’-二甲酸配合物的合成、结构及性质研究

2，2’-联吡啶-3，3’-二甲酸配合物的合成、结构及性质研究
　　It has been the hot research field to construct metal-organic coordination polymers with high orderly structure from organic ligands and metal ions in coordination chemistry, supramolecular chemistry and material science. The increasing interest in this field is justified not only by the particular beauty and intriguing structural diversities of the architectures, but also by their potential application as functional materials in optoelectronic, magnetic, catalytic and inclusive fields. The selection of multifunctional organic ligands and metal ion is crucial to the construction of desirable frameworks. It is of great importance to study of the relationship between design, structure and strong magnets property and establish proper synthetic strategies and rules leading to desirable supramolecular systems through controlling the assembly process of metal-organic frameworks. In this dissertation, 2,2’-bipyridine-3,3’-dicarboxylate was selected as the first ligand to synthesize eighteen new coordination two-dimensional or three-dimensional polymers through solution reactions with 2,2’-bipyridine, 1,2-di(4-pyridyl)ethylene as the second ligands.
　　Their crystal structures were characterized and properties were discussed.1. Nine new complexes(1-9) has been designed and synthesized with transition metal ions in solution reactions, [Zn(bpdc)(H2O)2]n (1), {[Cd(bpdc)(H2O)3]·2H2O}n (2), {[Co(bpdc)(H2O)3]·H2O}n(3), {[Co(bpdc)(H2O)3]·(dpe)0.5·(H2O)}n(4), [Mn(bpdc) (H2O)4]n (5), {[Mn2(bpdc)(2,2’-bpy)3]·(ClO4)2·(H2O)3}n (6), [Cu(bpdc)(H2O)2]n (7), [Ag2(bpdc)]n (8) and {[Mn(bpdc)(dpe)]·(CH3OH)·(H2O)2}n (9) (H2bpdc = 2,2’-bipyridine-3,3’-dicarboxylate acid, dpe=1,2-di(4-pyridyl)ethylene). Among of them, complexes (1)-(6) are one-dimensional chains, complexes (7)-(9) are two-dimensional networks. X-ray structural analysis revealed that 2,2’-bipyridine -3,3’-dicarboxylate acid has been found seven different coordinated modes. In addition, complexes 1 and 2 exhibit intense blue photoluminescence. The magnetic behaviour of complexes 3, 4, 5, 7 and 9 were studied and indicated the existence of antiferromagnetic interactions.2. Eight three-dimensional mixed metallic polymers were http://www.chinamagnets.biz/ synthesized by 2,2’-bipyridine-3,3’-dicarboxylate acid with transitional and lanthanide metals. {[CoNd2 (C12H6N2O4)3(NO3)2(H2O)8]·(C2H6O)(H2O)}n (10), {[NiTb2(C12H6NO4)3(NO3)2 (H2O)8]·3.0(H2O)}n (11), {[NiGd2(C12H6N2O4)3(NO3)2(H2O)8]·(C2H6O)·2.5(H2O)}n (12), {[NiSm2(C12H6N2O4)3(NO3)2(H2O)8]·2.5(H2O)}n (13), {[NiNd2(C12H6N2O4)3 (NO3)2(H2O)8]·3.5(H2O)}n (14), {[NiLa2(C12H6N2O4)3(NO3)2(H2O)8]·4(H2O)}n (15), {[CoSm2(C12H6N2O4)3(NO3)2(H2O)8]·3.5(H2O)}n (16), {[ZnLa2(C12H6N2O4)3(NO3)2 (H2O)8]·2(H2O)}n (17). The magnetic behaviours of complex 10 were studied andindicated the existence of antiferromagnetic interactions.3. The three-dimensional compound, {Na[Mg(H2O)6][Cu2(C12H6N2O4)2(N3)3]}n,has been synthesized and characterized with transitional and primary metal in solution. X-ray structural analysis revealed the azido ligand has exhibited the two bridged modes of EO and EE. The three-dimensional structure is bridged by double end-on (EO) and single end-to-end (EE) azido bridges. Magnetic measurement indictates antiferromagnetic coupling.