Syntheses, Structures And Properties Of Coordination Polymers Constructed From Biphenyldicarboxylic Acid And Organic Ligand Containing Nitrogen

The thesis is concern about the syntheses, structures and properties study of the biphenyldicarboxylato and pyridine dicarboxylato complexes. Herein, we successfully synthesized 23 novel complexes by means of hydrothermal condition and further characterized by X-ray single crystal diffraction, elemental analysis, IR, TG and magnetism analysis. The results are summarized as follows:First, based on 2,4’-biphenyldicarboxylic acid as primary ligand and three different flexible bis(imidazole) or bis(byridine) as ancillary ligands, we successfully constructed nine novel dimentional coordination polymers(1 and 2 section in chapter 2). Herein, compound 1 and 2,4 and 5 were assembled by tunning-up the mixture ratio in the reation species. Magnetic susceptibility measurement for compound 8 reveals that among the wheel-like binuclear Co2-ions exists an anti-ferromagnetic characterization.Not only limited to the assembly of monometallic polymers, we also constructed seven 3d-4f heterometallic coordination polymers by introducing 2,2’-bipyridine into the action system(the third section in chapter 2). Complexes 10-16 are characterized by a tetranuclear M2Ln2(M=Cu, Co) structures. Each tetranuclear M2Ln2 unit is coordinated by ten 2,4’-bpdc2- anions and two 2,2’-bpy to form a 2D stucture. Magnetic susceptibility measurement for 13,14 and 15 shows that among the tetranuclear unit exists anti-ferromagnetic behavior, while 16 takes on a ferrimagnetic behavior.Second, altering carboxyl group positon, we adopt 4,4’-biphenyldicarboxylic acid(4,4’-H2bpdc) to construct another series of coordination polymers(chapter 3). By introducing flexible bis(imidazole) ligands with a proper length into the reaction system, we successfully assembled two polyrotaxane-like polymers, which contain loops and rods that are interlaced in a parelleled fashion. The dimension of the loops formed by bix(or bimh) ligands and Co2+ ions is11.613A×6.919A, through which a Co-bpdc-Co rod just right pass. The polyrotaxane-like coordination polymers so far have been rare documented. In addition, when we combined 4.4’-H2bpdc and rigid bis(imidazole) ligand to gain a 5-connected 3-fold interpenetrating 3D framework with a unique 4466 topology. To the best of my knowledge, this is the first 5-connected 3-fold interpenetrating famework. Magnetic susceptibility measurement for 20 shows that among the trinuclear Mn3 unit exists an anti-ferromagnetic characterization.The third, based on N.O-contanning 2,3-pyridine dicarboxylic acid(2,3-H2pydc), we constructed three novel 3d-4f heterometallic polymers with the help of the auxiliary anions(chapter 4). of which compound 21 is a 3D porous Co-Dy coordination polymer with H2C2O4 as auxiliary ligand. Further magenetic analysis shows the compound take on an anti-ferromagnetic characterization.22 and 23 are 2D layer coordination polymers with Ln-carboxylato helical chain, which is rare in 3d-4f heterometallic complexes. Further the magenetic analysis of 23 shows the compound take on a ferromagnetic characterization.