Design,Synthesis And Fluorescence Properties Of Bis(8-hydroxyquinoline)-based Functional Complexes

Herein,five ligands based on 8-hydroxyquinoline skeletons with different structures and functions were synthesized.Based on coordination and supramolecular chemistry,A series of functional metal complexes with unique structures and properties were prepared via solvothermal method and room temperature reaction.The as-synthesized compounds were characterized by a variety of techniques,and the luminescence properties of coordination complexes had also been studied.This thesis includes the following four chapters.In chapter 1,the recent development of several functional complexes of different structural types(coordination polymer,coordinated cage,macrocyclic metal organic compoumd and cluster)was summarized.The challenges remained in this area were discussed.In chapter 2,a novel bis(8-hydroxyquinoline)rigid linear ligand L₁-H₂ was designed and synthesized by two-step reaction using 8-hydroxyquinaldine as starting material.In different solvent systems,four no vel coordination polymers 1-4 were prepared by treating different metal ions Mn(II),Cd(II)and Zn(II)with ligand L₁-H₂,respectively.Complexes 1-4 were characterized by various spectroscopic methods such as:X-ray single crystal diffraction,infrared spectroscopy,and X-Ray Powder Diffraction,etc.The roles of supramolecular interactions in the construction of their structures were discussed in detail;In addition,the luminescence properties of coordination polymers 1-4 had also been studied.In C hapter 3,two bis(8-hydroxyquinoline)flexible ligands L₂-H₂ and L₃-H₂were prepared by several steps.O ne novel coordinated cage 5 has been successfully synthesized by solvothermal methods.When ligand L₃-H₂was used instead of L₂-H₂under the same synthesis conditions of 5,two cage-like complexes 6 and 7 with larger cavities were obtained.By introducing two bipyridine auxiliary ligands(4,4'-BPy:4,4'-bipyridyl and B(Py)E:1,2-bis(4-pyridyl)ethene)in the reaction system,two coordinated cages 8 and 9 with similar dimer structures were successfully synthesized.These complexes were characterized by X-ray single crystal diffraction,infrared spectroscopy,and X-ray powder diffraction.The roles of supramolecular interactions in the construction of 5-9 were discussed in detail;What's more,the fluorescent properties of cage complexes 5-9 had been studied.In chapter 4,three bis(8-hydroxyquinoline)flexible ligands L₃-H₂,L₄-H₂ and L₅-H₂ were synthetized by several steps.Six novel coordination complexes 10-15were obtained by treating different metal ions Ag(I),Cd(II)and Zn(II)with these ligands,respectively.Among them,three one-dimensional chain-like coordination polymers 10-12 were prepared by treating flexible ligands L₃-H₂ and L₄-H₂with Ag(I)under alkaline conditions;In comparison,complexes 13-15 were synthesized by treating ligands L₄-H₂ and L₅-H₂ with Cd(II)and Zn(II)under non-alkaline conditions,respectively.In addition,the luminescent properties of these two ligands as well as the complexes 10-15 were also studied.