Synthesis, Crystal Structures And Properties Of Coordination Polymers Based On "V-shaped" And Triangle Carboxylate Ligands

Metal-organic frameworks (MOFs) have novel structures and the extensive applications in the optical, electrical, magnetic, catalysis, molecular recognition, adsorption, hydrogen storage materials. These applications make MOFs to attract the attention of many chemists. Two kinds of the flexible organic ligands which are4,4’-(phenylazanediyl)dibenzoic acid (H2L) and4,4’-(4-(pyridine-4-yl) phenylazanediyl)dibenzoic acid (H2PBA) are designed and synthesized in the thesis. H2L as a "V" shaped linker and H2PBA as a tripod ligand provide the possibility for the construction of the pore structure of coordination polymers.We successfully synthesized seven coordination polymers based on "V-shapes" flexible4,4’-(phenylazanediyl)dibenzoic acid and nitrogenous organic ligands as auxiliary ligands under hydrothermal(solvothermal) conditions.{[CdL(4,4’-bipy)·DMF}n (1),{Cd2(L)2(bpe)2}n (2){[CoL(4,4’-bipy)]·DMF}n (3) have the same coordination mode and the crystal structure. They have2D layer structures and Form ABAB accumulation.{[CoL(bpyb)0.5]·(H2O)2}n (4) includes [Co2(CO2)4]clusters and is not interspersed3D structure. With the topological viewpoint, the framework of4adopts the cds topology, a4-connected{65·8} net. Magnetic testing indicates antiferromagnetic coupling between Co ions.{[Cu4(μ3-OH)2(L)2]·DMF}n (5) has a unique crystal structure. These {Cu4}-based SBUs are connected to1D [Cu4(μ3-OH)4(CO2)4]n chains by two bridged carboxylate groups of two L ligands and two μ3-OH. The1D [Cu4(μ3-OH)4(CO2)4]n chains further are linked by L ligands into a3D framework. There are many larger pores size of12.050×9.302A in the crystal structure of compound5. Topology analys shows Schlafli symbol {44·611}. Magnetic testing indicates antiferromagnetic coupling between Cu ions. The{[Ni2O(L)2(bpp)2]·2DMA}n (6) has [Ni2O(CO)4] clusters and2D structures form3D structure by interlocking. The topological analysis of the6crystal structure displays schlafli symbol{33·410·5·6}. Complex{[NiL(bpe)1.5]·H2O}n (7) form1D+2D=3D structure with the role of the two ligands. The topology analysis of compound7reveals the Schlafli symbol{610}.[Co(PBA)2]·DMF}n (8) is syntheticed on the tripod ligand4,4’-(4-(pyridine-4-yl)phenylazanediyl)dibenzoic acid under hydrothermal (solvothermal) conditions. The every PBA ligand connect three [Co2(CO2)4] clusters to form a double interspersed3D net structure. The topological analysis of8crystal structure gives Schlafli symbols {4·62}2{42·610·83}. Between the Co ions interaction deplays antiferromagnetic coupling.