Syntheses And Properties Of Coordition Polymers Based On Aromatic Carboxylic Acids Ligand

Coordination polymers?CPs?is self-assembled into a new type of functional materials by coordination action with dual functions of machine materials and inorganic materials,in which metal ions as the node and organic ligands as the connector.As a new type of composite material,CPs have been shown great potential applications in fluorescent probes,organic catalysis,dye degradation and gas adsorption.In this paper,fourteen coordination polymers by utilizing mixed-linker methods have been constructed from4,4'-?1H-1,2,4-triazol-1-yl?methylenebis?benzonicacid??H₂TZMB?,tri?p-carboxyphenyl?phosphane oxide?H₃TPO?and a series of nitrogen-containing auxiliary ligands.And they have been characterized by X-ray single crystal diffraction,powder diffraction,IR,thermogravimetric analysis and elemental analysis were performed.The main research contents as follows:?1?CPs 1-5 were constructed based on 4,4'-?1H-1,2,4-triazol-1-yl?methylenebis?benzonic acid??H₂TZMB?and zinc/cadmium with d₁₀0 configuration.X-ray single crystal diffraction analysis shows that 1,2,and 5 are 3D framework structures.3 is formulated by its 2D layer structures by?…?stacking interactions further form an prolonged 3D supramolecular framework.4 is 2D framework structures.CPs 1,2,4 and 5 were analyzed by fluorescence and 3 was analyzed by adsorption.The results showed that 1 and 2 can selectively detect Fe³⁺,and the low of detection 2 was 2.56×10^-4.4 and 5 can selectively detect nitro compounds and could be used as candidate materials for fluorescent probes.3 can selectively absorb CO₂from CH₄,which is of great significance for controlling greenhouse effect.?2?CPs 6-9 were constructed based on 4,4'-?1H-1,2,4-triazol-1-yl?methylenebis?benzonic acid??H₂TZMB?and cobalt salts.X-ray single crystal diffraction analysis showed that 6,8and 9 were 3D framework,and the whole 7 is a 2D network structure with 2-node 3-,6-connected.The adsorption performance of 9 was studied.The adsorption capacity of 9 for hydrogen was 158.36 m_·³g^-1,and that for CO₂ were 58.64 cm_·³g^-1?273K?and 22.34 cm_·³g^-1??298K.The adsorption capacity of CH₄ were 15.79 cm_·³g^-1?273K?and 21.31 cm_·³g^-1?298K?.The ideal adsorption solution theory?IAST?was used to evaluate the selective adsorption of 9 on CH₄/CO₂ binary gas.The selectivity coefficient of natural gas is?CO₂/CH₄=0.05/0.95?and coal mine tunnel gas?CO₂/CH₄=0.5/0.5?are 12.60 and 19.34,respectively.The results show that 9 can be used as potential energy storage material and functional material to control greenhouse effect.?3?The tri?p-carboxyphenyl?phosphane oxide?H₃TPO?and five nitrogen-containing auxiliary ligands were selected to synthesize five novel complexes with structures 10-14.10and 11 are mononuclear 3D framework,13 is multi-core 3D structures,12 as dual-core 2D structures and 14 as mononuclear 2D structures.The results of gas adsorption showed that 10can selectively adsorb methyl blue,which as potential applications in the degradation of dyes.The fluorescence analysis of 12 was showed that 12 can selectively detect CrO₄^2-,Cr₂O₇^2-and Fe³⁺,showing a good application prospect for the detection of sewage in the environment.