Syntheses,structures And Properties Of Coordination Polymers Based On V-shaped And Triangle N-donor Ligands

This thesis consist of two parts:Firstly,we employed a V-shaped semi-rigid ligand,4,4’-bis（pyridine-4-yl）diphenyl ether（OPY）and five coordination polymers with distinct structural features were synthesized by hydrothermal method.Secondly,six coordination polymers 6-11 with novel frameworks and properties have been synthesized based on a semi-rigid triangle ligand[tris（4-（1H-imidazol-1-yl）phenyl）amine]（TIPA）by solvothermal method.1.Syntheses,structures,and properties of coordination polymers based on4,4’-bis（pyridine-4-yl）diphenyl ether（OPY）Solvothermal reactions of 4,4’-bis（pyridine-4-yl）diphenyl ether（OPY）and naphthalene-2,6-dicarboxylic acid（H₂ndc）,thiophene-2,5-dicarboxylic acid（H₂tda）,benzene-1,3,5-tricarboxylic acid（H₃btc）with transition salts yielded five complexes,namely,{[Cd（OPY）₂（ndc）（H₂O）]·H₂O}_n（1）,{[Cd（OPY）（tdc）（H₂O）]·H₂O}_n（2）,[Zn（OPY）（tdc）]_n（3）,[CuCl（OPY）]_n（4）,[Co（OPY）_1.5（Hbtc）]_n（5）.Compound 1 is a2-fold parallel interpenetrating network consist of two identical sets of 2D layer motifs and shows both polyrotaxane and polycatenane characters.The basic structure of compound 2 is a one-dimensional[Cd（OPY）₂（tdc）（H₂O）]_n chain of withμ₁–OPY on each side,which was extended to a three-dimensional supramolecular structure hydrogen bonds andπ–πstacking interactions.Compound 3 represent the first example of a five-fold interpenetrated 4³·6²·8-gis network topology.Compound 4represent the first example of a 2D→3D polycatenation structure via vertical interpenetration of two set layers.Compound 5 is a 3D pillar-layered-like framework,in which the OPY ligand adopts two different coordination modes not only expands dinuclear cobalt chain to a 3D framework,but also enhances the stability of compound 1.Magnetic measurements performed on 5 indicate the occurrence of weak antiferromagnetic coupling between the neighboring Co²⁺ions.2.Syntheses,structures,and properties of coordination polymers based on[tris（4-（1H-imidazol-1-yl）phenyl）amine]（TIPA）Six intriguing coordination polymers with unique topologies and properties have been synthesized by employed a triphenylamine based N-donor ligand and different carboxylic ligands,heptanedioic acid（H₂pim）,glutaric acid（H₂glu）,terephthalic acid（H₂bdc）,benzene-1,2,4,5-tetracarboxylic acid（H₄btc）.{[Zn（TIPA）·（pim）]·3H₂O]}_n（6）,{[Zn（TIPA）·（pim）_1/2]·2H₂O·NO₃]}_n（7）,{[Zn（TIPA）·（glu）]·2H₂O}_n（8）,{[Co₂（TIPA）₂·（bdc）₂·4H₂O]·H₂O·DMF}_n（9）,{[M（TIPA）（btec）_0.5]H₂O}_n,[M=Co（10）,Zn（11）]。Compound 6 is a 2D+2D→2D parallel entangle structure by penetrating and interlocking modes.Compound 7 and 6 were synthesized by the same starting materials,but 7 crystallizes in chiral space group and has a（10,3）-a,srs topological feature.Compound 8 is a four-fold interpenetrating 3D framework with dia topology.Compound 9 is a 2D→3D inclined interpenetrating net,in which the pim^2-anion withμ¹-η¹:η⁰ coordination mode bind to Co²⁺ion and distribute equally on each side of each 6³ layer.Compound 10 and 11 are isostructural.Both TIPA and btc^4-ligands acting as bidentate bridging ligand expand the dinuclear Co unit to a two-fold interpenetrated pcu topological network.The magnetic property measurement on 10indicates that there exists weak antiferromagnetic interactions amongst Co（II）ions within dinuclear Co unit.