Synthesis And Properties Of Coordination Polymers Based On Aniline Carboxylic Acids

During the past two or three decades,remarkable progress has been made in the research of the metal organic coordination polymer?CPs?,not only because of their fascinating topologies,but also due to their excellent properties and potential applications in the fields of gas storage and separation,luminescence,biomedicine,chemical sensors,ion exchange,molecular recognition and separation,magnetic materials,heterogeneous catalysis,and so on.Moreover,it has become an important research frontier and a new type of research field,and even begun to show the clues of commercial applications.Although a variety of CPs have been reported today,the design and directional synthesis of coordination polymers are still challenging due to various factors.In this article,by designing and synthesizing several different types of aniline organic carboxylic acid ligands,fourteen novel metal-organic coordination polymers were obtained under appropriate conditions,and their structures,luminescence and other properties were discussed.The main achievements were as follows:1.Six novel coordination polymers were prepared by newly synthesized V-type4,4'-trianiline dicarboxylic acid?H₂L?with different nitrogen ligands and transition metal cobalt in hydrothermal solvents,namely[CoL?1,3-bimb?]·H2O?1?,[Co₂L₂?bimp?_0.5]·3H₂O?2?,[Co₂L₂?1,4-bimb?₂]·2DMF?3?,[CoL?bibp?]·2DMF?4?,[CoL?bpmp?0.5]·H2O?5?,[Co2L2?bidpe?2]·H2O?6?.Their structures were analyzed and characterized by X-ray single crystal diffractometer,infrared and thermogravimetry.Compounds 1 and 2 gave a 2-fold interpenetrating three-dimensional?3D?supramolecular networks,3 exhibited a 4-fold interpenetrating 3D framework,4displayed a 3-fold interpenetrate 2D layer,5 showed a 3D framework,6 viewed of2-fold interpenetrate 1D cyclic chain.And their electrochemical properties were tested by cyclic voltammetry,the results showed that compounds 1-6 were electrochemically active substances with good electrochemical reversibility.2.Two coordination polymers,[CdL?bifu?]·H2O?7?,[Cd2L2?tipa?2]·3H2O?8?,were prepared from 4,4'-?phenylazanediyl?dibenzoic acid?H₂L?,metal cadmium,rigid and flexible nitrogen ligands under hydrothermal/solvent thermal conditions,and their structures were analyzed.The results showed that compound 7 displayed a 3-fold interpenetrate 3D framework,compound 8 showed a 2-fold interpenetrate 3D framework.It was found by fluorescence test that both compounds 7 and 8 could emit light,but compound 8 had better blue light emission characteristics and could be used as a fluorescence probe to detect Fe³⁺ions in aqueous solution.3.Six novel CPs were fabricated by the reaction of based on N,N'-bis?4-carbozylbenzyl?-4-aminotoluene?H₂L'?with varied different N-donor ligands and transition metal salts under hydrothermal/solvothermal conditions,namely[Mn?L'??bibp?]?9?,[Pb?L'??bibp?_0.5]?10?,[Cd₂?L'?₂?bibp?]·2H₂O?11?,[Ni?L'??bib?]?12?,[Mn?L'?2?bif?]?13?,[Zn2?L'??bibp?]·H2O?14?,their structures were characterized by X-ray single crystal diffractometer and crystal analysis software.The results showed that compounds 9,11 and 13 exhibited a 2D layered structure,compound 10 displayed a 3D supramolecular network structure,compound 12 showed a 3-fold interpenetrate 2D layer,compound 14 presented an 8-fold interpenetrating diamondoid networks with[4+4]mode.By studying the fluorescence property and adsorption property for organic dyes of compound 14,it also could be used as a fluorescent probe for Fe³⁺ions in aqueous solution,and efficiently adsorb methyl orange?MO?solution under natural light.