Heterocyclic Carboxylic Acids Containing Nitrogen And Oxygen And Transition Metal Ions Co²⁺, Zn²⁺, Ni²⁺, Mn^{2 Coordination Assembly And Properties Of +}

Metal organic frameworks,also called porous coordination polymers,have attracted great attentions during the past two decades due to their porosity,high specific surface area,unsaturated metal sites,the diversity of structure and functionability.Nowadays,MOFs have been successfully applied in the fields of gas storage,adsorption and separation,sensor,molecular sieve membrane,biological activity,luminescence and catalysis,etc.But how to extend their fields of application,MOFs are still needed to further explore and investigate.The syntheses of transition metal ion coordination polymers are mainly realized through the self-assembly process.Regulating and controlling the structures of coordination polymers via metal ions and auxilary ligands is one important strategy for the coordination polymers design and assembly.The purpose of the present thesis is to design a series of coordination polymers with novel structures based on the train of thought of regulating and controlling the structures of coordination polymers via metal ions and auxiliary ligands.Fourteen coordination polymers with one-dimensional,two-dimensional and three-dimensional structures were syhtheized through hydrothermal synthesis routes and process cooling to room temperature for regulating the structures of coordination polymers by using asymmetric aromatic carboxylic acid containing nitrogen and oxygen of 1,4-naphthalene diformate and 3,5-two pyridine carboxylic acid as main ligands,coordinated assembly with transition metal ions of Co2+,Zn2+,Ni2+,Mn2+,and introduing bbi,o-phenanthroline,terephthalic acid ligands as the auxiliary ligands.The compositions and structures of coordination polymers were determined by means of X-ray diffraction,infrared spectroscopy and thermogravimetric analysis,the arrangement mode of cooperation unit in the complexes,interaction,and the relationship between the structure and function were eluicdated by the deep analysis using the structural analysis software of olex2,diamond and TOPOS4.0.The structure characteristics were compared and discussed systematiclly,and the investiagtion on the magnetic susceptibility and fluorescence properties of coordination polymers were also carried out.The present works would provide experimental data,guidance and a theoretical model for the future R&D of the novel complexes.The works were briefly summarized as follows:1?Four novel transition metal ion Co(?)of {[Co(C12H10N4)2(H2O)4]·2C4H3O4}n(1),{Co(C12H8N2)4(C8H4O5)6(H2O)n}(2),{Co(KCB)2(bbi)2(H2O)}n(3),{CO2(KCB)2(H2O)5}n(4)were synthesized through self-assembly using 1,4-naphthalene formic acid and bbi as main ligands.The two-dimensional or three-dimensional mesh topology structures of complexes(1)(2)and(3)were formed by hydrogen bonding and partial ?...? packing interaction.The complex(4)contains the ?2-O bridge bond O,which makes the whole molecule form a three-dimensional network structure with a central symmetry,and perfectly interprets the characteristics of the cluster structure of?2-O and binuclear metal.The investigations on the magnetic properties of the four complexes illustrated that they all had weak antiferromagnetic properties.2?Five transition metal Zn(?)complexes of {Zn(bbi)2(C8H3NO6)2}n(5),{[Zn(bbi)(C7H3O4N)]·2H2O}n(6),{[Zn(bbi)1.5(H2O)2]·2NO3}·2H2O}n(7),{Zn(C8H4O5)(H2O)3}n(8),{[Zn8(?4-O)2(KCB)6(DMF)3]·DMF}n(9),were synthesized through self-assembly using 1,4-naphthalene formic acid and bbi as the main ligands;Complex(5)contained hydrogen bonds and ?...? packing,building a three-dimensional network structure.Complex(6)contained the bi-coordination modes of 3,5-pyridine formic acid,which plays an important role in the construction of network.Both complex(7)and(8)contained coordinated water molecules,which were easy to form hydrogen bonds with surrounding O atoms with higher electronegativity.The complex(9)of cluster compound was formed by the 1,4-naphthalene acid and two of the ?4-O bridge,having muliti-coordination modes,presenting a fascinating three-dimensional structure.It was found from the solid state fluorescence characterization that the complexes of(5)(6)and(9)had fluorescent properties and could be used as potential fluorescent materials.3?Seven complexes of transition metal Co2+,Zn2+,Ni2+,Mn2+(10-16)were synthesized through self-assembly using bbi and SCN-as ligands.The characterization analysis demonstrated that the three-dimensional network structures of the complexes were formed by the hydrogen bonds and the ?...? packing.Complexes of 10 and 11 showed a certain antiferromagnetism,while complexes of 12,13 and 14 exhibited weak ferromagnetism,these materials are potentially magnetic materials,paving the way for the future research.