Design,Synthese And Property Study Of Coordirnation Polymer Based On Nitrogen Ligands

The coordination polymers?CPs?is an important metal organic crystal material with high porosity,low density,large specific surface area,adjustable aperture and cutability.It has shown a good prospect and high research value in gas storage,adsorption and separation,drug release,sensor and driver,catalysis,optical materials and so on.Copper?I?-halide cluster based on coordination polymers have been widely used by researchers because of their low cost,well-structured,good optical properties and promising applications in solar energy conversion and OLED devices.In this paper,a four-tooth ligand 1,1,2,2-tetrakis?4-?1H-imidazol-1-yl?phenyl?ethylene?TIPE?containing nitrogen imidazoles was designed and synthesized.Two kinds of Copper?I?-halide cluster based on coordination polymers [Cu₄I?TIPE?₃].3I?1?and [Cu₄Cl?TIPE?₃]·3Cl?2?with three-dimensional framework were synthesized by solvating these nitrogen-containing imidazole ligands under solvent or hydrothermal conditions.The electrochemical behavior of Copper?I?-halide cluster based on coordination polymers was characterized by X-ray single crystal diffraction,elemental analysis,fluorescence spectroscopy,UV-Vis absorption spectroscopy,infrared spectroscopy,nuclear magnetic resonance spectroscopy and cyclic voltammetry.This paper consists of five chapters,the main research contents are as follows:In Chapter 1,maily focuses on the research progress of coordination polymers,synthesis methods,the influencing factors of coordination polymers and their applications in gas storage,heterogeneous catalysis and fluorescence sensing.And elaborated the basis and purpose of this paper.In Chapter 2,the nitrogen-containing ligands TIPE was synthesized by using Mc Murray reaction,electrophilic substitution and solid phase reaction.We characterized it by 1H-NMR spectroscopy.In Chapter 3,a new 3D coordination polymers,namely [Cu₄I?TIPE?₃].3I?1?,has been synthesized under hydrothermal condition.1 is a cation skeleton and the counter anions Iions,dispersing in the avoid space,which acts primarily as a balanced charge.Compared with 1,the emission bond of the ligand is slightly red-shifted.The luminescent spectrum of compound shows a strong blue fluorescence at room temperature.The experimental result indicates that it has quantitative detection performance for F-ions,and the detection limit of compound 1 towards F-ions is calculated to be 2.11×10-6 mol/L.In Chapter 4,a 3D new coordination polymers [Cu₄Cl?TIPE?₃].3Cl?2?has been synthesized in the presence of CuCl₂·2H₂O and TIPE ligand under hydrothermal condition.2 is a cation skeleton and the counter anions Cl-ions,dispersing in the avoid space,which acts primarily as a balanced charge.The PXRD patterns of samples indicates 2 exhibits excellent chemical stability in aqueous solutions with pH scale ranges from 1 to 11 and boiling water.Interestingly,2 show high catalytic activities for degradation of dyes,such as RhB,MB and MO under LED and natural light irradiation,and followed by the first order reaction kinetics.In addition,after three successive experiments under the same conditions,the good stability of 2 is confirmed by PXRD and FT-IR spectra,and studied the degradation mechanism.In Chapter 5,summarizes the research contents.