2,2 '- Bipyridine -3,3' - Dicarboxylate Complexes Synthesis, Structure And Nature Of The Study

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 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 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.